EP1432746A2 - Deodorants and anti-perspirants - Google Patents

Deodorants and anti-perspirants

Info

Publication number
EP1432746A2
EP1432746A2 EP01989525A EP01989525A EP1432746A2 EP 1432746 A2 EP1432746 A2 EP 1432746A2 EP 01989525 A EP01989525 A EP 01989525A EP 01989525 A EP01989525 A EP 01989525A EP 1432746 A2 EP1432746 A2 EP 1432746A2
Authority
EP
European Patent Office
Prior art keywords
deodorants
acid
antiperspirants
vinyl
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01989525A
Other languages
German (de)
French (fr)
Other versions
EP1432746B1 (en
Inventor
Matthias LÖFFLER
Roman MORSCHHÄUSER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Produkte Deutschland GmbH, Clariant GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1432746A2 publication Critical patent/EP1432746A2/en
Application granted granted Critical
Publication of EP1432746B1 publication Critical patent/EP1432746B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

  • the present invention relates to deodorants and antiperspirants containing comb-shaped copolymers based on acryloyldimethyltauric acid.
  • Deodorants and antiperspirants are presented in different forms, such as gels, sticks, creams, sprays or powders.
  • Cosmetic deodorants are used to remove body odor that arises when the odorless sweat is decomposed by microorganisms.
  • the usual cosmetic deodorants are based on different active principles.
  • antiperspirants the formation of sweat can be reduced by astringents - for example aluminum salts such as aluminum hydroxychloride.
  • astringents for example aluminum salts such as aluminum hydroxychloride.
  • the use of antimicrobial substances in cosmetic deodorants can reduce the bacterial flora on the skin. Ideally, only the odor-causing microorganisms should be effectively reduced.
  • the combination of astringents with antimicrobial substances is also common.
  • antiperspirant active ingredients are often not compatible with common constituents of deodorant cosmetic and pharmaceutical preparations.
  • deodorising sticks are usually formed from soap-glycol gels, since lower glycols and glycerin can form clear, transparent gels in the presence of sodium stearate, which can also absorb alcohol and water. Due to the alkalinity of the soaps, acidic active ingredients, for example aluminum hydroxychloride, cannot be incorporated into such carriers.
  • soap-free deodorants and antiperspirants have also been developed, e.g. based on liquid oils (e.g. paraffin oils, castor oil, isopropyl palmitate), which contain semi-solid ingredients (e.g. petroleum jelly, Lanolin), solid components (e.g. beeswax, ceresin, microcrystalline waxes or ozokerite) and / or high-melting waxes (e.g. camauba wax, candelilla wax) are thickened.
  • semi-solid ingredients e.g. petroleum jelly, Lanolin
  • solid components e.g. beeswax, ceresin, microcrystalline waxes or ozokerite
  • high-melting waxes e.g. camauba wax, candelilla wax
  • AMPS acryloyldimethyltauric acid
  • the invention relates to deodorants and antiperspirants containing at least one copolymer, obtainable by radical copolymerization of
  • D) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization
  • E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization
  • Component selected from one of groups D) to G) is copolymerized.
  • the copolymers according to the invention preferably have a molecular weight of 10 3 g / mol to 10 9 g / mol, particularly preferably 10 4 to 10 7 g / mol, particularly preferably 5 * 10 4 to 5 * 10 6 g / mol.
  • the Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinklare (Acrylamidopropyl-2-methyl-2-sulfonic acid).
  • the Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ and / or NH 4 + salts are preferred.
  • the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts are likewise preferred, the alkyl substituents of the amines being independent of one another
  • the degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization from above is particularly preferred 80%.
  • the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.
  • All olefinically unsaturated, non-cationic monomers whose reaction parameters permit copolymerization with acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective reaction media can be used as comonomers B).
  • Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a carbon number of 1 to 30.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.
  • Preferred counterions are Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or
  • Tetraalkylammonium residues where the alkyl substituents of the amines independently of one another are (C 1 -C 22 ) alkyl residues or (C 2 -C 1o) hydroxyalkyl residues.
  • alkyl substituents of the amines independently of one another are (C 1 -C 22 ) alkyl residues or (C 2 -C 1o) hydroxyalkyl residues.
  • one to three times ethoxylated ammonium compounds with different degrees of ethoxylation can also be used.
  • the degree of neutralization of the carboxylic acids can be between 0 and 100%.
  • comonomers B) are open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, Hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) e
  • the proportion by weight of comonomers B), based on the total mass of the copolymers, can be 0 to 99.8% by weight and is preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.
  • Suitable comonomers C) are all olefinically unsaturated monomers with a cationic charge which are capable of forming copolymers in the selected reaction media with acryloyldimethyltauric acid or its salts.
  • the resulting distribution of the cationic charges over the chains can be statistical, alternating, block-like or gradient-like.
  • the cationic comonomers C) also include those which carry the cationic charge in the form of a betaine, zwitterionic or amphoteric structure.
  • Comonomers C) in the sense of the invention are also amino-functionalized precursors which are converted into their corresponding quaternary (e.g.
  • reaction with dimethyl sulfate, methyl chloride), zwitterionic (e.g. reaction with hydrogen peroxide), betaine (e.g. reaction with chloroacetic acid) or amphoteric derivatives by polymer-analogous reactions can.
  • Particularly preferred comonomers C) are diallyldimethylammonium chloride (DADMAC),
  • [2-methacrylamidoethyl] trimethyl ammonium chloride [2- (acrylamido) ethyl] trimethylammonium chloride, N-methyl-2-vinylpyridinium chloride N-methyl-4-vinylpyridinium chloride dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, methacryloylethyl-N-oxide and / or methacryloylethyl-betaine.
  • the proportion by weight of the comonomers C), based on the total mass of the copolymers, can be 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20% by weight.
  • Suitable polymerizable, silicon-containing components D) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case.
  • the distribution of the individual silicone-containing monomers across the resulting polymer chains does not necessarily have to be statistical.
  • the formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention. Combinations of two or more different silicone-containing representatives are also possible.
  • the use of silicone-containing components with two or more polymerization-active groups leads to the formation of branched or cross-linked structures.
  • Preferred silicone-containing components are those of the formula (I).
  • R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means.
  • a suitable chemical bridge Z is required to connect the silicone-containing polymer chain to the reactive end group R 1 .
  • Preferred bridges Z are -O-, - ((-C-C 5 o) alkylene) -, - ((C 6 -C 30 ) arylene) -, - ((C 5 -C 8 ) cycloalkylene) -, - (( C ⁇ -C 5 o) alkenylene) -, - (polypropylene oxide) n -, - (polyethylene oxide) 0 -, - (polypropylene oxide) n (polyethylene oxide) 0 -, where n and o independently of one another represent numbers from 0 to 200 and the distribution the EO / PO units can be statistical or block-shaped. Also suitable as Z bridge groups
  • the polymer middle part is represented by silicone-containing repeat units.
  • radicals R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -O-CH 3 ,
  • the indices w and x represent stoichiometric coefficients which, independently of one another, are 0 to 500, preferably 10 to 250.
  • the distribution of the repeating units over the chain can not only be purely statistical, but can also be block-like, alternating or gradient-like.
  • R 2 can symbolize on the one hand an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 5 o) hydrocarbon radical (linear or branched) or -OH, -NH 2 , -N (CH 3 ) 2 , -R 7 or for the structural unit
  • R 7 stands for further Si-containing groups. Preferred R 7 radicals are
  • R 2 represents an element of the group [-ZR 1 ], it is a matter of difunctional monomers which can be used for crosslinking the resulting polymer structures.
  • Formula (I) describes not only vinylically functionalized, silicone-containing
  • Particularly preferred silicone-containing components are the following acrylic or methacrylic modified silicone-containing components:
  • the content of silicon-containing components can be up to 99.8% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
  • Suitable polymerizable, fluorine-containing components E) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case.
  • the distribution of the individual fluorine-containing monomers across the resulting polymer chains does not necessarily have to be statistical.
  • the formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention.
  • Combinations of two or more different fluorine-containing components E) are also possible, it being clear to the expert that monofunctional representatives are responsible for education comb-shaped structures lead, whereas di-, tri-, or polyfunctional components E) lead to at least partially cross-linked structures.
  • Preferred fluorine-containing components E) are those of the formula (II).
  • R represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymeric structures by radical means.
  • a suitable chemical bridge Y is required in order to connect the fluorine-containing moiety to the reactive end group R 1 is a suitable chemical bridge Y is required.
  • Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 -O-, -O-SO2-O-.
  • R and s are stoichiometric coefficients that
  • Preferred fluorine-containing components E) according to formula (II) are perfluorohexylethanol methacrylate, perfluorohexoylpropanol methacrylate,
  • Perfluoroctylpropanolyl-polypropylene-glycol ether methacrylate Based on the total mass of the copolymer, the content of fluorine-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
  • the macromonomers F) are at least simple olefinically functionalized polymers with one or more discrete repeating units and a number average molecular weight greater than or equal to 200 g / mol. Mixtures of chemically different macromonomers F) can also be used in the copolymerization.
  • the macromonomers are polymeric structures which are composed of one or more repeating unit (s) and have a molecular weight distribution which is characteristic of polymers.
  • Preferred macromonomers F) are compounds of the formula (III).
  • R 1 represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means.
  • a suitable bridging group Y is required to bind the polymer chain to the reactive end group.
  • Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 O-, -O-SO 2 -O-, -O-SOz-O-, -O-SO-O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH- and -N (CH 3 ) -, particularly preferably -O-.
  • the polymeric middle part of the macromonomer is represented by the discrete repeat units A, B, C and D.
  • Preferred repeating units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile,
  • indices v, w, x and z in formula (III) represent the stoichiometric coefficients relating to the repeating units A, B, C and D.
  • v, w, x and z are independently 0 to 500, preferably 1 to 30, the The sum of the four coefficients must be ⁇ 1 on average.
  • the distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.
  • R 2 represents a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 5 o) hydrocarbon radical, OH, -NH 2 , -N (CH 3 ) 2 or is the same as the structural unit [-YR 1 ].
  • R 2 equal to [-YR 1 ]
  • these are difunctional macromonomers which are suitable for crosslinking the copolymers.
  • Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).
  • R 3 , R 4 , R 5 and R 6 are independently hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 3 o) hydrocarbon radicals.
  • R 3 and R 4 are preferably H or —CH 3 , particularly preferably H;
  • R 5 is H or -CH 3 ;
  • Re is equal to n-aliphatic a, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 30) - hydrocarbon radical.
  • v and w are again the stoichiometric coefficients relating to the ethylene oxide units (EO) and propylene oxide units (PO), v and w are independently 0 to 500, preferably 1 to 30, the sum of v and w on average having to be> 1.
  • the distribution of the EO and PO units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.
  • Y stands for the bridges mentioned above.
  • Further particularly preferred macromonomers F) have the following structure according to formula (IV):
  • Also particularly suitable as macromonomers F) are esters of (meth) acrylic acid with
  • Genapol ® types are products from Clariant, GmbH.
  • the molecular weight of the macromonomers F) is preferably 200 g / mol to 10 6 g / mol, particularly preferably 150 to 10 4 g / mol and particularly preferably 200 to 5000 g / mol.
  • suitable macromonomers up to 99.8% by weight can be used.
  • Fractions of 1 to 20% by weight and 75 to 95% by weight are particularly preferred.
  • Preferred copolymers are those which can be obtained by copolymerizing at least that of components A), C) and D).
  • copolymers are those which can be obtained by copolymerizing at least components A), C) and E).
  • copolymers are those which can be obtained by copolymerizing at least components A), D) and F).
  • copolymers are those which can be obtained by copolymerizing at least components A) and F).
  • copolymers are those which can be obtained by copolymerizing at least components A) and D).
  • the copolymerization is carried out in the presence of at least one polymeric additive G), the additive G) before the actual copolymerization is added to the polymerization medium in whole or in part in solution.
  • the use of several additives G) is also according to the invention.
  • Crosslinked additives G) can also be used.
  • the additives G) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium.
  • additive G) has several functions.
  • additive G is statistically attacked by active radicals in accordance with the generally known mechanism of graft copolymerization.
  • suitable additives G) have the property of changing the solution parameters of the copolymers which form during the radical polymerization reaction in such a way that the average molecular weights are shifted to higher values.
  • additives G are homo- and copolymers soluble in water and / or alcohols, preferably in t-butanol. Copolymers are also to be understood as meaning those with more than two different types of monomers.
  • Particularly preferred additives G) are homopolymers and copolymers of N-vinylformamide, N-vinyl acetamide, N-vinyl pyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N-vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.
  • additives G are polyvinylpyrrolidones (such as Luviskol K15 ®, K20 ® and K30 ® from BASF), poly (N-vinylformamides), poly (N-vinylcaprolactams) and copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.
  • the molecular weight of the additives G) is preferably 10 2 to 10 7 g / mol, particularly preferably 0.5 * 10 4 to 10 6 g / mol.
  • the amount of polymeric additive G) used is, based on the total mass of the monomers to be polymerized during the copolymerization, preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight .-%.
  • the copolymers according to the invention are crosslinked, i.e. they contain comonomers with at least two polymerizable vinyl groups.
  • Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives. Trimethylolpropane triacrylate (TMPTA) is particularly preferred as the crosslinking agent.
  • the proportion by weight of crosslinking comonomers, based on the total mass of the copolymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.
  • All organic or inorganic solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which advantageously permit the formation of medium or high molecular weights.
  • Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol; Hydrocarbons with 1 to 30 carbon atoms and mixtures of the aforementioned compounds.
  • the polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C., particularly preferably between 10 and 100 ° C., both under normal pressure and under elevated or reduced pressure. If necessary, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.
  • High-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators such as organic peroxides, for example benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as azodiisobutyronitrile (AIBN), can be used to initiate the polymerization.
  • organic peroxides for example benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as azodiisobutyronitrile (AIBN)
  • AIBN azodiisobutyronitrile
  • inorganic peroxy compounds such as (NH) 2 S 2 O 8 , K 2 S 2 O 8 or H 2 O 2 , optionally in combination with reducing agents (for example sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or Redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.
  • reducing agents for example sodium bisulfite, ascorbic acid, iron (II) sulfate etc.
  • Redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.
  • All solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which permit the formation of high molecular weights. Water and lower, tertiary alcohols or hydrocarbons
  • t-butanol is used as the reaction medium.
  • Mixtures of two or more representatives of the potential solvents described are of course also in accordance with the invention.
  • This also includes emulsions of immiscible solvents (e.g. water / hydrocarbons).
  • immiscible solvents e.g. water / hydrocarbons.
  • all types of reaction control which lead to the polymer structures according to the invention are suitable (solution polymerization, emulsion process, precipitation process, high-pressure process, suspension process, bulk polymerization, gel polymerization, etc.).
  • Precipitation polymerization is particularly suitable, particularly preferably precipitation polymerization in tert-butanol.
  • the following list shows 67 copolymers which are particularly suitable for the formulation of the agents according to the invention.
  • the various copolymers No. 1 to No. 67 can be obtained according to the following production processes 1, 2, 3 and 4.
  • Butanol can be produced.
  • the monomers were initially introduced into t-butanol, the reaction mixture was rendered inert, and the reaction was then started after heating to 60 ° C. by adding the corresponding t-butanol-soluble initiator (preferably dilauroyl peroxide). After the reaction has ended (2 hours), the polymers are isolated by suction removal of the solvent and subsequent vacuum drying.
  • the corresponding t-butanol-soluble initiator preferably dilauroyl peroxide
  • Process 2 These polymers can be prepared in water using the gel polymerization process.
  • the monomers are dissolved in water, the reaction mixture is rendered inert, and the reaction is then started after heating to 65 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 ⁇ 8 ).
  • suitable initiator or initiator systems preferably Na 2 S 2 ⁇ 8 .
  • the polymer gels are then crushed and the polymers isolated after drying.
  • These polymers can be prepared in water using the emulsion process.
  • the monomers are mixed in a water / organ mixture.
  • Solvent preferably cyclohexane
  • emulsifier emulsifier
  • the reaction mixture is rendered inert using N 2 and the reaction is then started after heating to 80 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 ⁇ 8 ).
  • suitable initiator or initiator systems preferably Na 2 S 2 ⁇ 8 .
  • the polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.
  • polymers are after the solution process in organic solvents (preferably toluene, for example also partially alcohols) can be prepared.
  • organic solvents preferably toluene, for example also partially alcohols
  • the monomers preferably dilauroyl peroxide
  • the reaction mixture is rendered inert and then the reaction after initial heating äuf ⁇ 70 ° C by the addition of suitable initiators or initiator systems started.
  • the polymers are isolated by evaporation of the solvent and subsequent vacuum drying.
  • the copolymers are water-soluble or water-swellable.
  • the described, optionally feasible grafting of the copolymers with other polymers leads to products with a particular polymer morphology which result in optically clear gels in aqueous systems.
  • a potential disadvantage of the copolymers without grafting is a more or less strong opalescence in aqueous solution. This is based on previously unavoidable, over-crosslinked polymer fractions that arise during the synthesis and are not sufficiently swollen in water. As a result, light-scattering particles form, the size of which is well above the wavelength of visible light and are therefore the cause of opalescence.
  • the described, optionally feasible grafting process makes the formation of cross-linked
  • Silicon-modified copolymers can take over the functions of silicone oils in part or in full.
  • the copolymers can reduce or avoid the use of silicones.
  • the deodorants and antiperspirants according to the invention contain, based on the finished compositions, preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight of the copolymers.
  • the agents according to the invention preferably contain 0.01 to 89% by weight, particularly preferably 5 to 50% by weight, particularly preferably 10 to 30% by weight of water.
  • the agents according to the invention preferably contain up to 10% by weight, preferably 1 to 6% by weight, of glycerol.
  • the agents according to the invention preferably contain antimicrobial active substances which inhibit the sweat-decomposing microorganisms or the sweat-decomposing esterase enzyme.
  • antimicrobial active substances which inhibit the sweat-decomposing microorganisms or the sweat-decomposing esterase enzyme.
  • antimicrobial agents are preferably suitable as antimicrobial agents
  • agents according to the invention preferably contain the antimicrobial agents in amounts of up to 50% by weight, particularly preferably 0.01 to 10% by weight, particularly preferably 0.1 to 10% by weight.
  • the agents according to the invention preferably contain astringents.
  • Preferred astringents are oxides, preferably magnesium oxide, aluminum oxide, titanium dioxide, zirconium dioxide and zinc oxide, oxide hydrates, preferably aluminum oxide hydrate (boehmite) and hydroxides, preferably calcium, magnesium, aluminum, titanium, zirconium or zinc.
  • the agents according to the invention preferably contain the astringent active ingredients in amounts of 0 to 50% by weight, particularly preferably 0.01 to 10% by weight and particularly preferably 0.1 to 10% by weight.
  • the agents according to the invention further preferably contain gelling agents.
  • Suitable gelling agents are all surface-active substances which, when dissolved in the liquid phase, form a network structure and thus solidify the liquid phase.
  • Suitable gelling agents are e.g. mentioned in WO 98/58625.
  • Preferred gelling agents are metal salts of fatty acids, preferably with 12 to 22 carbon atoms, for example sodium stearate, sodium palmitate, sodium laurate, sodium arachidates, sodium behenate, potassium stearate, potassium palmitate, sodium myristate, potassium palmitate, aluminum monostearate, hydroxy fatty acids, for example 12-hydroxystearic acid, 16-lauryl acid, 16-lauryl acid, Hydroxyhexadecanoylklare; fatty acid amides; fatty acid; Dibenzalsorbit and alcohol-soluble polyamides and polyacrylamides or mixtures thereof.
  • the agents according to the invention preferably contain 0.01 to 20% by weight, particularly preferably 0.1 to 10% by weight, particularly preferably 1 to 8% by weight and very particularly preferably 3 to 7% by weight of gelling agents.
  • the agents according to the invention contain additional alcohols.
  • Preferred alcohols are alkoxylated alcohols with preferably 1 to 80, particularly preferably 3 to 20, alkoxy groups and at least one free hydroxyl group.
  • polyethylene glycols with a relative molecular weight below 2000 are polyethylene glycols with a relative molecular weight below 2000.
  • use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred.
  • the agents according to the invention preferably contain 5 to 90% by weight, particularly preferably 5 to 80% by weight and particularly preferably 20 to 60% by weight of alcohol.
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as fragrance or perfume oils.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropylate, stally.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cycllamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the ionones, alpha-isomethyl ionone and methyl cedryl ketone , to the alcohols anethole, citronellol, eugenol, geranion, linalool, phenylethyl alcohol and terpineol
  • Hydrocarbons mainly include the terpenes and balms. Mixtures of different fragrances are preferably used, which together produce an appealing fragrance.
  • Perfume oils can also contain natural fragrance mixtures, such as are available from plant or animal sources, e.g. Pine, citrus, jasmine, lily, rose, or ylang-ylang oil.
  • Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil and ladanum oil.
  • the agents according to the invention can contain, as further auxiliaries and additives, oil bodies, emulsifiers and co-emulsifiers, superfatting agents, moisturizing agents, stabilizers, biogenic agents (local anesthetics, antibiotics,
  • Oil body means any fatty substance that is liquid at room temperature (25 ° C).
  • the fat phase can comprise one or more oils, which are preferably selected from the following oils:
  • Silicone oils volatile or non-volatile, linear, branched or ring-shaped, possibly organically modified, phenyl silicones, silicone resins and rubbers which are solid or liquid at room temperature: b) mineral oils, such as paraffin or petroleum jelly oil c) oils of animal origin, such as Perhydrosqualene or lanolin; d) oils of vegetable origin, such as liquid triglycerides, for example sunflower, corn, soybean, rice, jojoba, babusscu, pumpkin, grape seed, sesame, walnut, apricot, macadamia, avocado, Sweet almond, cuckoo, castor oil, triglycerides of caprylic / capric acids, olive oil, peanut oil, rapeseed oil and coconut oil; e) synthetic oils, such as purcellin oil, isoparaffins, linear and / or branched fatty alcohols and fatty acid esters, preferably Guerbet alcohols having 6 to 18, preferably 8 to 10, carbon atoms;
  • Suitable nonionic co-emulsifiers are, inter alia, addition products of 0 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and on sorbitan or sorbitol esters; (-C 2 -C 18 ) fatty acid monoesters and diesters of adducts of 0 to 30 mol of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and, if appropriate, their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters, such as Polyglycerol poly
  • Suitable ionogenic co-emulsifiers are e.g. anionic emulsifiers, such as mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers, such as mono-, di- and tri-alkyl quats and their polymeric derivatives.
  • Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
  • polyethoxylated lanolin derivatives such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides
  • foam stabilizers for example, isopropyl palmitate, glycerin and / or sorbitol are available as a moisturizing substance.
  • Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or zinc stearate can be used.
  • Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.
  • the agents according to the invention can be mixed with conventional ceramides, pseudoceramides, fatty acid-N-alkylpolyhydroxyalkylamides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances as a care additive.
  • cellulose ethers and other cellulose derivatives eg carboxymethyl cellulose, hydroxyethyl cellulose
  • gelatin starch and starch derivatives
  • sodium alginates e.g., sodium alginates, fatty acid polyethylene glycol esters, agar-agar, tragacanth or dextrins are known.
  • polymers such as, for example, polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers of the above compounds, including their various salts and esters.
  • These polymers can optionally be cross-linked or uncross-linked.
  • Suitable UV filters are e.g. 4-aminobenzoic acid
  • vitamin E superoxide dismutase
  • vitamin C ascorbic acid
  • Suitable preservatives are phenoxyethanol, parabens, pentanediol or sorbic acid.
  • the dyes which can be used are those which are suitable and approved for cosmetic purposes.
  • the deodorants and antiperspirants are preferably lotions, creams, pens (also multi-phase pens), sprays, roll-on preparations and powders.
  • the agents according to the invention preferably have a pH of 2 to 12, particularly preferably 3 to 8.
  • copolymers used in the examples are representatives of the particularly preferred copolymers No. 1 to No. 67 already listed in the description.
  • the preparation was carried out according to methods 1, 2, 3 or 4 given there using the preferred initiators and solvents.
  • phase B Slowly add phase B to phase A while stirring at room temperature.
  • Example 4 O / W Deodorant Lotion A Teginacid H 3.0% Glyceryl Stearate / Ceteth-20
  • Example 5 Non-alcoholic deodorant roll-on (opaque)
  • Zinc ricinoleate / tetrahydroxypropyl-ethylenediamine / Laureth-3 / propylene glycol Polyethylene glycol (3) lauryl ether 1, 0%
  • phase B dissolve pH 4 to 5 with slow stirring.
  • Example 7 Deodorant emulsion

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Abstract

The invention relates to deodorants and anti-perspirants containing at least one copolymer, which can be obtained by radical copolymerisation of: A) acryloyldimethyltaurine acid and/or acryloyldimethyltaurates, B) optionally, one or more additional olefinically unsaturated, non-cationic comonomers, C) optionally, one or more olefinically unsaturated, cationic comonomers, D) optionally, one or more components containing silicon, E) optionally, one or more components containing fluorine and F) optionally, one or more macromonomers, G) the copolymerisation taking place in the presence of at least one polymeric additive, H) provided that component A) is copolymerised with at least one component selected from one of the groups D) to G).

Description

Beschreibung description
Deodorantien und AntiperspirantienDeodorants and antiperspirants
Die vorliegende Erfindung betrifft Deodorantien und Antiperspirantien, enthaltend kammförmige Copolymere auf Basis von Acryloyldimethyltaurinsäure.The present invention relates to deodorants and antiperspirants containing comb-shaped copolymers based on acryloyldimethyltauric acid.
Deodorantien und Antiperspirantien werden in unterschiedlichen Formen, wie Gele, Sticks, Cremes, Sprays oder Puder dargeboten. Kosmetische Deodorierungsmittel dienen dazu, Körpergeruch zu beseitigen, der entsteht, wenn der an sich geruchlose Schweiß durch Mikroorganismen zersetzt wird. Den üblichen kosmetischen Deodorantien liegen unterschiedliche Wirkprinzipien zugrunde.Deodorants and antiperspirants are presented in different forms, such as gels, sticks, creams, sprays or powders. Cosmetic deodorants are used to remove body odor that arises when the odorless sweat is decomposed by microorganisms. The usual cosmetic deodorants are based on different active principles.
In sogenannten Antiperspirantien kann durch Adstringenzien- beispielsweise Aluminiumsalze wie Aluminiumhydroxychlorid - die Bildung des Schweißes reduziert werden. Durch die Verwendung antimikrobieller Stoffe in kosmetischen Deodorantien kann die Bakterienflora auf der Haut reduziert werden. Dabei sollten im Idealfall nur die Geruch verursachenden Mikroorganismen wirksam reduziert werden. Auch die Kombination von Adstringenzien mit antimikrobiell wirksamen Stoffen ist gebräuchlich.In so-called antiperspirants, the formation of sweat can be reduced by astringents - for example aluminum salts such as aluminum hydroxychloride. The use of antimicrobial substances in cosmetic deodorants can reduce the bacterial flora on the skin. Ideally, only the odor-causing microorganisms should be effectively reduced. The combination of astringents with antimicrobial substances is also common.
Insbesondere antiperspirierende Wirkstoffe sind häufig mit gängigen Bestandteilen deodorierender kosmetischer und pharmazeutischer Präparate nicht kompatibel. So werden deodorierende Stifte in der Regel aus Seifen-Glykol-Gelen gebildet, da niedere Glykole und Glycerin in Gegenwart von Natriumstearat klare, transparente Gele bilden können, welche zusätzlich Alkohol und Wasser aufnehmen können. Aufgrund der Alkalinität der Seifen können saure Wirkstoffe, beispielsweise Aluminiumhydroxychlorid in solche Träger nicht eingearbeitet werden.In particular, antiperspirant active ingredients are often not compatible with common constituents of deodorant cosmetic and pharmaceutical preparations. For example, deodorising sticks are usually formed from soap-glycol gels, since lower glycols and glycerin can form clear, transparent gels in the presence of sodium stearate, which can also absorb alcohol and water. Due to the alkalinity of the soaps, acidic active ingredients, for example aluminum hydroxychloride, cannot be incorporated into such carriers.
Wegen dieser Nachteile wurden auch seifenfreie Deodorantien und Antiperspirantien entwickelt, z.B. auf Basis flüssiger Öle (z.B. Paraffinöle, Ricinusöl, Isopropylpalmitat), die mit halbfesten Bestandteilen (z.B. Vaseline, Lanolin), festen Bestandteilen (z.B. Bienenwachs, Ceresin, mikrokristallinen Wachse bzw. Ozokerit) und/ oder hochschmelzenden Wachsen (z.B. Camaubawachs, Candelillwachs) verdickt sind. Nachteilig ist, dass wasserlösliche Wirkstoffe häufig nicht genug fettlöslich sind und folglich nur unzureichend in kosmetische Grundlagen eingebaut werden können. Andererseits ist ein gewisser Wassergehalt durchaus erwünscht, um die Verträglichkeit der Mittel mit der menschlichen Haut oder um die Löslichkeit von salzartigen Inhaltsstoffen zu verbessern. Als flüssige Öle eignen sich Silikonöle, die ein sehr angenehmes Hautgefühl der Mittel ergeben. Diese sind jedoch sehr teuer und weisen Nachteile bei der stabilen Einarbeitung wasserlöslicher Wirkstoffe auf und sind in Mitteln mit höheren Wassergehalten schwer formulierbar.Because of these disadvantages, soap-free deodorants and antiperspirants have also been developed, e.g. based on liquid oils (e.g. paraffin oils, castor oil, isopropyl palmitate), which contain semi-solid ingredients (e.g. petroleum jelly, Lanolin), solid components (e.g. beeswax, ceresin, microcrystalline waxes or ozokerite) and / or high-melting waxes (e.g. camauba wax, candelilla wax) are thickened. It is disadvantageous that water-soluble active ingredients are often not sufficiently soluble in fat and consequently cannot be adequately incorporated into cosmetic bases. On the other hand, a certain water content is quite desirable in order to improve the compatibility of the agents with human skin or to improve the solubility of salt-like ingredients. Silicone oils are suitable as liquid oils, which give the agents a very pleasant feeling on the skin. However, these are very expensive and have disadvantages in the stable incorporation of water-soluble active ingredients and are difficult to formulate in mediums with higher water contents.
Überraschend wurde nun gefunden, dass sich eine neue Klasse von Kammpolymeren auf Basis von Acryloyldimethyltaurinsäure (AMPS) - die sich sowohl als Verdicker, Konsistenzgeber, Emulgator, Solubilisator, Dispergator, Gleitmittel, Haftmittel, Conditioner und/oder Stabilisator eignen - hervorragend zur Formulierung von Deodorantien und Antiperspirantien eignen.Surprisingly, it has now been found that a new class of comb polymers based on acryloyldimethyltauric acid (AMPS) - which are suitable as thickeners, consistency agents, emulsifiers, solubilizers, dispersants, lubricants, adhesives, conditioners and / or stabilizers - are outstandingly suitable for the formulation of deodorants and antiperspirants.
Gegenstand der Erfindung sind Deodorantien und Antiperspirantien, enthaltend mindestens ein Copolymer, erhältlich durch radikalische Copolymerisation vonThe invention relates to deodorants and antiperspirants containing at least one copolymer, obtainable by radical copolymerization of
A) Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten,A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates,
B) gegebenenfalls einem oder mehreren weiteren olefinisch ungesättigten, nicht kationischen, gegebenenfalls vernetzenden, Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und einB) optionally one or more further olefinically unsaturated, non-cationic, optionally crosslinking, comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and one
Molekulargewicht kleiner 500 g/mol besitzen,Have a molecular weight of less than 500 g / mol,
C) gegebenenfalls einem oder mehreren olefinisch ungesättigten, kationischen Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen,C) optionally one or more olefinically unsaturated, cationic comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol,
D) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, siliziumhaltigen Komponente(n), E) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, fluorhaltigen Komponente(n),D) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization, E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization,
F) gegebenenfalls einem oder mehreren einfach oder mehrfach olefinisch ungesättigten, gegebenenfalls vernetzenden, Makromonomeren, die jeweils mindestens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom besitzen und ein zahlenmittleres Molekulargewicht größer oder gleich 200 g/mol aufweisen, wobei es sich bei den Makromonomeren nicht um eine siliziumhaltige Komponente D) oder fluorhaltige Komponente E) handelt,F) optionally one or more mono- or poly-olefinically unsaturated, optionally crosslinking, macromonomers, each of which has at least one oxygen, nitrogen, sulfur or phosphorus atom and have a number average molecular weight greater than or equal to 200 g / mol, where the Macromonomers are not silicon-containing component D) or fluorine-containing component E),
G) wobei die Copolymerisation gegebenenfalls in Gegenwart mindestens eines polymeren Additivs mit zahlenmittleren Molekulargewichten von 200 g/mol bis 109 g/mol erfolgt, H) mit der Maßgabe, dass die Komponente A) mit mindestens einerG) where the copolymerization is optionally carried out in the presence of at least one polymeric additive with number-average molecular weights of 200 g / mol to 10 9 g / mol, H) with the proviso that component A) with at least one
Komponente ausgewählt aus einer der Gruppen D) bis G) copolymerisiert wird.Component selected from one of groups D) to G) is copolymerized.
Die erfindungsgemäßen Copolymere besitzen bevorzugt ein Molekulargewicht von 103 g/mol bis 109 g/mol, besonders bevorzugt von 104 bis 107 g/mol, insbesondere bevorzugt 5*104 bis 5*106 g/mol.The copolymers according to the invention preferably have a molecular weight of 10 3 g / mol to 10 9 g / mol, particularly preferably 10 4 to 10 7 g / mol, particularly preferably 5 * 10 4 to 5 * 10 6 g / mol.
Bei den Acryloyldimethyltauraten kann es sich um die anorganischen oder organischen Salze der Acryloyldimethyltaurinsäure (Acrylamidopropyl-2-methyl-2- sulfonsäure) handeln. Bevorzugt werden die Li+-, Na+-, K+-, Mg++-, Ca++-, Al+++- und/oder NH4 +-Salze. Ebenfalls bevorzugt sind die Monoalkylammonium-, Dialkylammonium-, Trialkylammonium- und/oder Tetraalkylammoniumsalze, wobei es sich bei den Alkylsubstituenten der Amine unabhängig voneinander umThe Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinsäure (Acrylamidopropyl-2-methyl-2-sulfonic acid). The Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ and / or NH 4 + salts are preferred. The monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts are likewise preferred, the alkyl substituents of the amines being independent of one another
(Cι-C22)-Alkylreste oder (C2-Cι0)-Hydroxyalkylreste handelt. Weiterhin sind auch ein bis dreifach ethoxylierte Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad bevorzugt. Es sollte angemerkt werden, dass auch Mischungen von zwei- oder mehreren der oben genannten Vertreter im Sinne der Erfindung sind.(-C 22 -C) alkyl radicals or (C 2 -C 0 ) -hydroxyalkyl radicals. Furthermore, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation are preferred. It should be noted that mixtures of two or more of the above representatives are also within the meaning of the invention.
Der Neutralisationsgrad der Acryloyldimethyltaurinsäure kann zwischen 0 und 100 % betragen, besonders bevorzugt ist ein Neutralisationsgrad von oberhalb 80 %.The degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization from above is particularly preferred 80%.
Bezogen auf die Gesamtmasse der Copolymere beträgt der Gehalt an Acryloyldimethyltaurinsäure bzw. Acryloyldimethyltauraten mindestens 0,1 Gew.-%, bevorzugt 20 bis 99,5 Gew.-%, besonders bevorzugt 50 bis 98 Gew.-%.Based on the total mass of the copolymers, the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.
Als Comonomere B) können alle olefinisch ungesättigten, nicht kationischen Monomere eingesetzt werden, deren Reaktionsparameter eine Copolymerisation mit Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten in den jeweiligen Reaktionsmedien erlauben.All olefinically unsaturated, non-cationic monomers whose reaction parameters permit copolymerization with acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective reaction media can be used as comonomers B).
Als Comonomere B) bevorzugt sind ungesättigte Carbonsäuren und deren Anhydride und Salze, sowie deren Ester mit aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen Alkoholen mit einer Kohlenstoffzahl von 1 bis 30.Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a carbon number of 1 to 30.
Als ungesättigte Carbonsäuren besonders bevorzugt sind Acrylsäure, Methacrylsäure, Styrolsulfonsäure, Maleinsäure, Fumarsäure, Crotonsäure, Itaconsäure und Seneciosäure. Als Gegenionen bevorzugt sind Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 +, Monoalkyl- ammonium-, Dialkylammonium-, Trialkylammonium- und/oderParticularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid. Preferred counterions are Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or
Tetraalkylammonium-reste, wobei es sich bei den Alkylsubstituenten der Amine unabhängig voneinander um (Cι-C22)-Alkylreste oder (C2-Cιo)-Hydroxyalkylreste handelt. Zusätzlich können auch ein bis dreifach ethoxylierte Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad Anwendung finden. Der Neutralisationsgrad der Carbonsäuren kann zwischen 0 und 100 % betragen.Tetraalkylammonium residues, where the alkyl substituents of the amines independently of one another are (C 1 -C 22 ) alkyl residues or (C 2 -C 1o) hydroxyalkyl residues. In addition, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation can also be used. The degree of neutralization of the carboxylic acids can be between 0 and 100%.
Als Comonomere B) weiterhin bevorzugt sind offenkettige N-Vinylamide, bevorzugt N-Vinylformamid (VIFA), N-Vinylmethylformamid, N-Vinylmethylacetamid (VIMA) und N-Vinylacetamid; cyclische N-Vinylamide (N-Vinyllactame) mit einer Ringgröße von 3 bis 9, bevorzugt N-Vinylpyrrolidon (NVP) und N-Vinylcaprolactam; Amide der Acryl- und Methacrylsäure, bevorzugt Acrylamid, Methacrylamid, N,N-Dimethyl- acrylamid, N,N-Diethylacrylamid und N,N-Diisopropylacrylamid; alkoxylierte Acryl- und Methacrylamide, bevorzugt Hydroxyethylmethacrylat, Hydroxymethylmethacrylamid, Hydroxyethylmethacrylamid, Hydroxypropylmethacrylamid und Bernsteinsäuremono-[2-(methacryloyloxy)- ethylester]; N,N-Dimethylaminomethacrylat; Diethylamino-methylmethacrylat; Acryl- und Methacrylamidoglykolsäure; 2- und 4-Vinylpyridin; Vinylacetat; Methacrylsäureglycidylester; Styrol; Acrylnitril; Vinylchlorid; Stearylacrylat; Laurylmethacrylat; Vinylidenchlorid; und/oder Tetrafluorethylen. Als Comonomere B) ebenfalls geeignet sind anorganische Säuren und deren Salze und Ester. Bevorzugte Säuren sind Vinylphosphonsäure, Vinylsulfonsäure, Allylphosphonsäure und Methallylsulfonsäure.Also preferred as comonomers B) are open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, Hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; Diethylamino-methyl; Acrylic and methacrylamidoglycolic acid; 2- and 4-vinyl pyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; Vinyl chloride; stearyl; lauryl; vinylidene chloride; and / or tetrafluoroethylene. Also suitable as comonomers B) are inorganic acids and their salts and esters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid and methallylsulfonic acid.
Der Gewichtsanteil der Comonomere B), bezogen auf die Gesamtmasse der Copolymere, kann 0 bis 99,8 Gew.-% betragen und beträgt bevorzugt 0,5 bis 80 Gew.-%, besonders bevorzugt 2 bis 50 Gew.-%.The proportion by weight of comonomers B), based on the total mass of the copolymers, can be 0 to 99.8% by weight and is preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.
Als Comonomere C) kommen alle olefinisch ungesättigten Monomere mit kationischer Ladung in Frage, die in der Lage sind, in den gewählten Reaktionsmedien mit Acryloyldimethyltaurinsäure oder deren Salze Copolymere zu bilden. Die dabei resultierende Verteilung der kationischen Ladungen über die Ketten hinweg kann statistisch, alternierend, block- oder gradientenartig sein. Es sei darauf hingewiesen werden, dass unter den kationischen Comonomeren C) auch solche zu verstehen sind, die die kationische Ladung in Form einer betainischen, zwitterionischen, oder amphoteren Struktur tragen. Comonomere C) im Sinne der Erfindung sind auch aminofunktionalisierte Precursor, die durch polymeranaloge Reaktionen in Ihre entsprechenden quaternären (z.B. Reaktion mit Dimethylsulfat, Methylchlorid), zwitterionischen (z.B. Reaktion mit Wasserstoffperoxid), betainischen (z.B. Reaktion mit Chloressigsäure), oder amphoteren Derivate überführt werden können.Suitable comonomers C) are all olefinically unsaturated monomers with a cationic charge which are capable of forming copolymers in the selected reaction media with acryloyldimethyltauric acid or its salts. The resulting distribution of the cationic charges over the chains can be statistical, alternating, block-like or gradient-like. It should be pointed out that the cationic comonomers C) also include those which carry the cationic charge in the form of a betaine, zwitterionic or amphoteric structure. Comonomers C) in the sense of the invention are also amino-functionalized precursors which are converted into their corresponding quaternary (e.g. reaction with dimethyl sulfate, methyl chloride), zwitterionic (e.g. reaction with hydrogen peroxide), betaine (e.g. reaction with chloroacetic acid) or amphoteric derivatives by polymer-analogous reactions can.
Besonders bevorzugt als Comonomere C) sind Diallyldimethylammoniumchlorid (DADMAC),Particularly preferred comonomers C) are diallyldimethylammonium chloride (DADMAC),
[2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC),[2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),
[2-(Acryloyloxy)ethyl]trimethylammoniumchlorid,[2- (acryloyloxy) ethyl] trimethylammonium chloride,
[2-Methacrylamidoethyl]trimethylammoniumchlorid, [2-(Acrylamido)ethyl]trimethylammoniumchlorid, N-Methyl-2-vinylpyridiniumchlorid N-Methyl-4-vinylpyridiniumchlorid Dimethylaminoethylmethacrylat, Dimethylaminopropylmethacrylamid, Methacryloylethyl-N-oxid und/oder Methacryloylethyl-betain.[2-methacrylamidoethyl] trimethyl ammonium chloride, [2- (acrylamido) ethyl] trimethylammonium chloride, N-methyl-2-vinylpyridinium chloride N-methyl-4-vinylpyridinium chloride dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, methacryloylethyl-N-oxide and / or methacryloylethyl-betaine.
Der Gewichtsanteil der Comonomeren C) kann, bezogen auf die Gesamtmasse der Copolymere, 0,1 bis 99,8 Gew.-%, bevorzugt 0,5 bis 30 Gew.-% und besonders bevorzugt 1 bis 20 Gew.-% betragen.The proportion by weight of the comonomers C), based on the total mass of the copolymers, can be 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20% by weight.
Als polymerisationsfähige, siliziumhaltige Komponenten D) sind alle mindestens einfach olefinisch ungesättigten Verbindungen geeignet, die unter den jeweils gewählten Reaktionsbedingungen zur radikalischen Copolymerisation befähigt sind. Dabei muss die Verteilung der einzelnen silikonhaltigen Monomere über die entstehenden Polymerketten hinweg nicht notwendigerweise statistisch erfolgen. Auch die Ausbildung von beispielsweise block- (auch multiblock-) oder gradientenartigen Strukturen ist im Sinne der Erfindung. Kombinationen von zwei oder mehreren unterschiedlichen silikonhaltigen Vertretern sind auch möglich. Die Verwendung von silikonhaltigen Komponenten mit zwei oder mehr polymerisationsaktiven Gruppen führt zum Aufbau verzweigter oder vernetzter Strukturen.Suitable polymerizable, silicon-containing components D) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case. The distribution of the individual silicone-containing monomers across the resulting polymer chains does not necessarily have to be statistical. The formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention. Combinations of two or more different silicone-containing representatives are also possible. The use of silicone-containing components with two or more polymerization-active groups leads to the formation of branched or cross-linked structures.
Bevorzugte silikonhaltige Komponenten sind solche gemäß Formel (I).Preferred silicone-containing components are those of the formula (I).
R1 - Z- [(Si(R3R4)-O-)w-(Si(R5R6)-O)x-]- R2 (I)R 1 - Z- [(Si (R 3 R 4 ) -O-) w - (Si (R 5 R 6 ) -O) x -] - R 2 (I)
Dabei stellt R1 eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen dar, die zum Aufbau polymerer Strukturen auf radikalischem Wege geeignet ist. Bevorzugt stellt R1 einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl-(CH2=CH-CO-), Methacryl- (CH2=C[CH3]-CO-), Crotonyl-, Senecionyt-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest dar. Zur Anbindung der silikonhaltigen Polymerkette an die reaktive Endgruppe R1 ist eine geeignete chemische Brücke Z erforderlich. Bevorzugte Brücken Z sind -O-, -((Cι-C5o)Alkylen)-, -((C6-C30) Arylen)-, -((C5-C8) Cycloalkylen)-, -((Cι-C5o)Alkenylen)-, -(Polypropylenoxid)n-, -(Polyethylenoxid)0-, -(Polypropylenoxid)n(Polyethylenoxid)0-, wobei n und o unabhängig voneinander Zahlen von 0 bis 200 bedeuten und die Verteilung der EO/PO-Einheiten statistisch oder blockförmig sein kann. Weiterhin geeignet als Brückegruppierungen Z sindR 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means. R 1 preferably represents a vinyl, allyl, methallyl, methylvinyl, acrylic (CH 2 = CH-CO-), methacrylic (CH 2 = C [CH 3 ] -CO-), crotonyl, senecionyt , Itaconyl, maleinyl, fumaryl or styryl radical. A suitable chemical bridge Z is required to connect the silicone-containing polymer chain to the reactive end group R 1 . Preferred bridges Z are -O-, - ((-C-C 5 o) alkylene) -, - ((C 6 -C 30 ) arylene) -, - ((C 5 -C 8 ) cycloalkylene) -, - (( Cι-C 5 o) alkenylene) -, - (polypropylene oxide) n -, - (polyethylene oxide) 0 -, - (polypropylene oxide) n (polyethylene oxide) 0 -, where n and o independently of one another represent numbers from 0 to 200 and the distribution the EO / PO units can be statistical or block-shaped. Also suitable as Z bridge groups
-((C1-Cιo)Alkyl)-(Si(OCH3)2)- und -(Si(OCH3)2)-.- ((C 1 -Cιo) alkyl) - (Si (OCH 3 ) 2 ) - and - (Si (OCH 3 ) 2 ) -.
Der polymere Mittelteil wird durch silikonhaltige Wiederholungseinheiten repräsentiert.The polymer middle part is represented by silicone-containing repeat units.
Die Reste R3, R4, R5 und R6 bedeuten unabhängig voneinander -CH3, -O-CH3,The radicals R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -O-CH 3 ,
-C6H5 oder -O-C6H5.-C 6 H 5 or -OC 6 H 5 .
Die Indizes w und x repräsentieren stöchiometrische Koeffizienten, die unabhängig voneinander 0 bis 500, bevorzugt 10 bis 250, betragen. Die Verteilung der Wiederholungseinheiten über die Kette hinweg kann nicht nur rein statistisch, sondern auch blockartig, alternierend oder gradientenartig sein kann.The indices w and x represent stoichiometric coefficients which, independently of one another, are 0 to 500, preferably 10 to 250. The distribution of the repeating units over the chain can not only be purely statistical, but can also be block-like, alternating or gradient-like.
R2 kann einerseits einen aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (Cι-C5o)-Kohlenwasserstoffrest symbolisieren (linear oder verzweigt) oder -OH, -NH2, -N(CH3)2, -R7 oder für die StruktureinheitR 2 can symbolize on the one hand an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 5 o) hydrocarbon radical (linear or branched) or -OH, -NH 2 , -N (CH 3 ) 2 , -R 7 or for the structural unit
[-Z-R1] stehen. Die Bedeutung der beiden Variablen Z und R1 wurde bereits erklärt. R7 steht für weitere Si-haltige Gruppierungen. Bevorzugte R7-Reste sind[-ZR 1 ] are available. The meaning of the two variables Z and R 1 has already been explained. R 7 stands for further Si-containing groups. Preferred R 7 radicals are
-O-Si(CH3)3, -O-Si(Ph)3, -O-Si(O-Si(CH3)3)2CH3) und -O-Si(O-Si(Ph)3)2Ph).-O-Si (CH 3 ) 3 , -O-Si (Ph) 3 , -O-Si (O-Si (CH 3 ) 3 ) 2CH 3 ) and -O-Si (O-Si (Ph) 3 ) 2 Ph).
Wenn R2 ein Element der Gruppe [-Z-R1] darstellt, handelt es sich um difunktionelle, Monomere, die zur Vernetzung der entstehenden Polymerstrukturen herangezogen werden können.If R 2 represents an element of the group [-ZR 1 ], it is a matter of difunctional monomers which can be used for crosslinking the resulting polymer structures.
Formel (I) beschreibt nicht nur vinylisch funktionalisierte, silikonhaltigeFormula (I) describes not only vinylically functionalized, silicone-containing
Polymerspezies mit einer polymertypischen Verteilung, sondern auch definiertePolymer species with a typical polymer distribution, but also defined
Verbindungen mit diskreten Molekulargewichten.Discrete molecular weight compounds.
Besonders bevorzugte silikonhaltige Komponenten sind die folgenden acrylisch- oder methacrylisch modifizierten silikonhaltigen Komponenten: Particularly preferred silicone-containing components are the following acrylic or methacrylic modified silicone-containing components:
Methacryloxyproplydimethylsilyl endgeblockte Polydimethylsiloxane (f=2 bis 500)Methacryloxyproplydimethylsilyl endblocked polydimethylsiloxanes (f = 2 to 500)
Methacryloxypropyl endgeblockte Polydimethylsiloxane (f= 2 bis 500 bis)Methacryloxypropyl endblocked polydimethylsiloxanes (f = 2 to 500 to)
Vinyldimethoxysilyl endgeblockte Polydimethylsiloxane (f = 2-500)Vinyldimethoxysilyl endblocked polydimethylsiloxanes (f = 2-500)
Bezogen auf die Gesamtmasse der Copolymere kann der Gehalt an siliziumhaltigen Komponenten bis 99,8 Gew.-%, bevorzugt 0,5 bis 30 Gew.-%, insbesondere bevorzugt 1 bis 20 Gew.-%, betragen.Based on the total mass of the copolymers, the content of silicon-containing components can be up to 99.8% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
Als polymerisationsfähige, fluorhaltige Komponenten E) sind alle mindestens einfach olefinisch ungesättigten Verbindungen geeignet, die unter den jeweils gewählten Reaktionsbedingungen zur radikalischen Copolymerisation befähigt sind. Dabei muss die Verteilung der einzelnen fluorhaltigen Monomere über die entstehenden Polymerketten hinweg nicht notwendigerweise statistisch erfolgen. Auch die Ausbildung von beispielsweise block- (auch multiblock-) oder gradientenartigen Strukturen ist im Sinne der Erfindung. Kombinationen von zwei oder mehreren unterschiedlichen, fluorhaltigen Komponenten E) ist auch möglich, wobei dem Experten klar ist, dass monofunktionelle Vertreter zur Bildung kammförmiger Strukturen führen, wohingegen di-, tri-, oder polyfunktionelle Komponenten E) zu zumindest teilvernetzten Strukturen führen.Suitable polymerizable, fluorine-containing components E) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case. The distribution of the individual fluorine-containing monomers across the resulting polymer chains does not necessarily have to be statistical. The formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention. Combinations of two or more different fluorine-containing components E) are also possible, it being clear to the expert that monofunctional representatives are responsible for education comb-shaped structures lead, whereas di-, tri-, or polyfunctional components E) lead to at least partially cross-linked structures.
Bevorzugte fluorhaltige Komponenten E) sind solche gemäß Formel (II).Preferred fluorine-containing components E) are those of the formula (II).
R1-Y-CrH2rCsF2sCF3 (II)R 1 -YC r H 2r C s F 2s CF 3 (II)
Dabei stellt R eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen dar, die zum Aufbau polymerer Strukturen auf radikalischem Wege geeignet ist. Bevorzugt stellt R1 ein Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl- (CH2=CH-CO-), Methacryl- (CH2=C[CH3]-CO-), Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest, besonders bevorzugt einen Acryl- und Methacrylrest, dar. Zur Anbindung der fluorhaltigen Gruppierung an die reaktive Endgruppe R1 ist eine geeignete chemische Brücke Y erforderlich. Bevorzugte Brücken Y sind -O-, -C(O)-, -C(O)-O-, -S-, -O-CH2-CH(O-)-CH2OH, -O-CH2-CH(OH)-CH2-O-, -O-SO2-O-. -O-S(O)-O-, -PH-, -P(CH3)-, -PO3-, -NH-, -N(CH3)-, -O-(C C5o)Alkyl-O-, -O-Phenyl-O-, -O-Benzyl-O-, -O-(C5-C8)Cycloalkyl-O-, -O-(Cι-C5o)Alkenyl-O-, -O-(CH(CH3)-CH2-O)n-, -O-(CH2-CH2-O)n- und -O-ttCH-GHz-OMCHrCHz-OWo-, wobei n, m und 0 unabhängig voneinander Zahlen von 0 bis 200 bedeuten und die Verteilung der EO- und PO-Einheiten statistisch oder blockförmig sein kann. Bei r und s handelt es sich um stöchiometrische Koeffizienten, die unabhängig voneinander Zahlen von 0 bis 200 bedeuten.R represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymeric structures by radical means. R 1 is preferably vinyl, allyl, methallyl, methylvinyl, acrylic (CH 2 = CH-CO-), methacrylic (CH 2 = C [CH 3 ] -CO-), crotonyl, senecionyl , itaconyl, maleyl, fumaryl or styryl radical, particularly preferably an acrylic and methacryloyl radical. in order to connect the fluorine-containing moiety to the reactive end group R 1 is a suitable chemical bridge Y is required. Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 -O-, -O-SO2-O-. -OS (O) -O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH-, -N (CH 3 ) -, -O- (CC 5 o) alkyl-O- , -O-phenyl-O-, -O-benzyl-O-, -O- (C 5 -C 8 ) cycloalkyl-O-, -O- (Cι-C 5 o) alkenyl-O-, -O- (CH (CH 3 ) -CH 2 -O) n -, -O- (CH 2 -CH 2 -O) n - and -O-ttCH-GHz-OMCHrCHz-OWo-, where n, m and 0 are independent of each other Numbers from 0 to 200 mean and the distribution of the EO and PO units can be statistical or block-shaped. R and s are stoichiometric coefficients that independently represent numbers from 0 to 200.
Bevorzugte fluorhaltige Komponenten E) gemäß Formel (II) sind Perfluorhexylethanol-methacrylat, Perfluorhexoylpropanol-methacrylat,Preferred fluorine-containing components E) according to formula (II) are perfluorohexylethanol methacrylate, perfluorohexoylpropanol methacrylate,
Perfluoroctyethanol-methacrylat, Perfluoroctylpropanol-methacrylat, Perfluorhexylethanolylpolygycolether-methacrylat,Perfluorooctyethanol methacrylate, perfluorooctylpropanol methacrylate, perfluorohexylethanolyl polyglycol ether methacrylate,
Perfluorhexoyl-propanolyl-poly-[ethylglykol-co-propylenglycolether]-acrylat,Perfluorhexoyl-propanolyl-poly [ethylene glycol-co-propylene glycol] acrylate,
Perfluoroctyethanolyl-poly-[ethylglykol-blockco-propylenglycolether]-methacrylat,Perfluoroctyethanolyl-poly [ethylene glycol-block co-propylene glycol] methacrylate,
Perfluoroctylpropanolyl-polypropylen-glycolether-methacrylat. Bezogen auf die Gesamtmasse des Copolymeren kann der Gehalt an fluorhaltigen Komponenten bis 99,9 Gew.-%, bevorzugt 0,5 bis 30 Gew.-%, insbesondere bevorzugt 1 bis 20 Gew.-%, betragen.Perfluoroctylpropanolyl-polypropylene-glycol ether methacrylate. Based on the total mass of the copolymer, the content of fluorine-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
Bei den Makromonomeren F) handelt sich um mindestens einfach olefinisch funktionalisierte Polymere mit einer oder mehreren diskreten Wiederholungseinheiten und einem zahlenmittleren Molekulargewicht größer oder gleich 200 g/mol. Bei der Copolymerisation können auch Mischungen chemisch unterschiedlicher Makromonomere F) eingesetzt werden. Bei den Makromonomeren handelt es sich um polymere Strukturen, die aus einer oder mehreren Wiederholungseinheit(en) aufgebaut sind und eine für Polymere charakteristische Molekulargewichtsverteilung aufweisen. Bevorzugt als Makromonomere F) sind Verbindungen gemäß Formel (III).The macromonomers F) are at least simple olefinically functionalized polymers with one or more discrete repeating units and a number average molecular weight greater than or equal to 200 g / mol. Mixtures of chemically different macromonomers F) can also be used in the copolymerization. The macromonomers are polymeric structures which are composed of one or more repeating unit (s) and have a molecular weight distribution which is characteristic of polymers. Preferred macromonomers F) are compounds of the formula (III).
R1 - Y - [(A)v - (B)w - (C)χ - (D)_] - R2 (III)R 1 - Y - [(A) v - (B) w - (C) χ - (D) _] - R 2 (III)
R1 stellt eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen dar, die zum Aufbau polymerer Strukturen auf radikalischem Wege geeignet sind. Bevorzugt stellt R1 einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl- (CH2=CH-CO-), Methacryl- (CH2=C[CH3]-CO-), Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest dar. Zur Anbindung der Polymerkette an die reaktive Endgruppe ist eine geeignete verbrückende Gruppe Y erforderlich. Bevorzugte Brücken Y sind -O-, -C(O)-, -C(O)-O-, -S-, -O-CH2-CH(O-)-CH2OH, -O-CH2-CH(OH)-CH2O-, -O-SO2-O-, -O-SOz-O-, -O-SO-O-, -PH-, -P(CH3)-, -PO3-, -NH- und -N(CH3)-, besonders bevorzugt -O-.R 1 represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means. R 1 preferably represents a vinyl, allyl, methallyl, methylvinyl, acrylic (CH 2 = CH-CO-), methacrylic (CH 2 = C [CH 3 ] -CO-), crotonyl, senecionyl , Itaconyl, maleinyl, fumaryl or styryl radical. A suitable bridging group Y is required to bind the polymer chain to the reactive end group. Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 O-, -O-SO 2 -O-, -O-SOz-O-, -O-SO-O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH- and -N (CH 3 ) -, particularly preferably -O-.
Der polymere Mittelteil des Makromonomeren wird durch die diskreten Wiederholungseinheiten A, B, C und D repräsentiert. Bevorzugte Wiederholungseinheiten A,B,C und D leiten sich ab von Acrylamid, Methacrylamid, Ethylenoxid, Propylen- oxid, AMPS, Acrylsäure, Methacrylsäure, Methylmethacrylat, Acrylnitril,The polymeric middle part of the macromonomer is represented by the discrete repeat units A, B, C and D. Preferred repeating units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile,
Maleinsäure, Vinylacetat, Styrol, 1,3-Butadien, Isopren, Isobuten, Diethylacrylamid und Diisopropylacrylamid. Die Indizes v, w, x und z in Formel (III) repräsentieren die stöchiometrische Koeffizienten betreffend die Wiederholungseinheiten A, B, C und D. v, w, x und z betragen unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, wobei die Summe der vier Koeffizienten im Mittel ≥ 1 sein muss. Die Verteilung der Wiederholungseinheiten über die Makromonomerkette kann statistisch, blockartig, alternierend oder gradientenartig sein. R2 bedeutet einen linearen oder verzweigten aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (Cι-C5o)-Kohlenwasser- stoffrest, OH, -NH2, -N(CH3)2 oder ist gleich der Struktureinheit [-Y-R1]. Im Falle von R2 gleich [-Y-R1] handelt es sich um difunktionelle Makromonomere, die zur Vernetzung der Copolymere geeignet sind.Maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide. The indices v, w, x and z in formula (III) represent the stoichiometric coefficients relating to the repeating units A, B, C and D. v, w, x and z are independently 0 to 500, preferably 1 to 30, the The sum of the four coefficients must be ≥ 1 on average. The distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like. R 2 represents a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 5 o) hydrocarbon radical, OH, -NH 2 , -N (CH 3 ) 2 or is the same as the structural unit [-YR 1 ]. In the case of R 2 equal to [-YR 1 ], these are difunctional macromonomers which are suitable for crosslinking the copolymers.
Besonders bevorzugt als Makromonomere F) sind acrylisch- oder methacrylisch monofunktionalisierte Alkylethoxylate gemäß Formel (IV).Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).
R3, R4, R5 und R6 bedeuten unabhängig voneinander Wasserstoff oder n-aliphatische, iso-aliphatische, olefinische, cycloaliphatische, arylaliphatische oder aromatische (Cι-C3o)-Kohlenwasserstoffreste.R 3 , R 4 , R 5 and R 6 are independently hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 3 o) hydrocarbon radicals.
Bevorzugt sind R3 und R4 gleich H oder -CH3, besonders bevorzugt H; R5 ist gleich H oder -CH3; und Re ist gleich einem n-aliphatischen, iso-aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (C1-C30)- Kohlenwasserstoffrest. v und w sind wiederum die stöchiometrischen Koeffizienten betreffend die Ethylenoxideinheiten (EO) und Propylenoxideinheiten (PO), v und w betragen unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, wobei die Summe aus v und w im Mittel > 1 sein muss. Die Verteilung der EO- und PO-Einheiten über die Makromonomerkette kann statistisch, blockartig, alternierend oder gradientenartig sein. Y steht für die obengenannten Brücken. Weiterhin insbesondere bevorzugte Makromonomeren F) haben die folgende Struktur gemäß Formel (IV):R 3 and R 4 are preferably H or —CH 3 , particularly preferably H; R 5 is H or -CH 3 ; and Re is equal to n-aliphatic a, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 30) - hydrocarbon radical. v and w are again the stoichiometric coefficients relating to the ethylene oxide units (EO) and propylene oxide units (PO), v and w are independently 0 to 500, preferably 1 to 30, the sum of v and w on average having to be> 1. The distribution of the EO and PO units over the macromonomer chain can be statistical, block-like, alternating or gradient-like. Y stands for the bridges mentioned above. Further particularly preferred macromonomers F) have the following structure according to formula (IV):
Weiterhin als Makromonomere F) insbesondere geeignet sind Ester der (Meth)acrylsäure mitAlso particularly suitable as macromonomers F) are esters of (meth) acrylic acid with
(Cιo-Cι8)-Fettalkoholpolyglykolethern mit 8 EO-Einheiten (Genapol® C-080) Cn-Oxoalkoholpolyglykolethem mit 8 EO-Einheiten (Genapol® UD-080) (Ci2-C14)-Fettalkoholpolyglykolethern mit 7 EO-Einheiten (Genapol® LA-070) (Ci2-Cι4)-Fettalkoholpolyglykolethern mit 11 EO-Einheiten (Genapol® LA-110) (Ci6-Cι8)-Fettalkoholpolyglykolethem mit 8 EO-Einheiten (Genapol® T-080) (Ci6-Cι8)-Fettalkoholpolyglykolethem mit 15 EO-Einheiten (Genapol® T-150) (Ci6-C1δ)-Fettalkoholpolyglykolethern mit 11 EO-Einheiten (Genapol® T-110) (Ci6-C18)-Fettalkoholpolyglycolethem mit 20 EO-Einheiten (Genapol® T-200) (Ci6-Cι8)-Fettalkoholpolyglykolethem mit 25 EO-Einheiten (Genapol® T-250) (Cι8-C22)-Fettalkoholpolyglykolethern mit 25 EO-Einheiten und/oder iso-(Ci6-Cι8)-Fettalkoholpolyglykolethern mit 25 EO-Einheiten.(Cιo-Cι 8 ) fatty alcohol polyglycol ethers with 8 EO units (Genapol ® C-080) Cn-oxo alcohol polyglycol ethers with 8 EO units (Genapol ® UD-080) (Ci 2 -C 14 ) fatty alcohol polyglycol ethers with 7 EO units ( Genapol ® LA-070) (Ci 2 -Cι 4 ) fatty alcohol polyglycol ethers with 11 EO units (Genapol ® LA-110) (Ci 6 -Cι 8 ) fatty alcohol polyglycol ethers with 8 EO units (Genapol ® T-080) (Ci 6 -Cι 8 ) fatty alcohol polyglycol ether with 15 EO units (Genapol ® T-150) (Ci 6 -C 1δ ) fatty alcohol polyglycol ethers with 11 EO units (Genapol ® T-110) (Ci 6 -C 18 ) fatty alcohol polyglycol ethers with 20 EO units (Genapol ® T-200) (Ci 6 -Cι 8 ) - Fatty alcohol polyglycol ether with 25 EO units (Genapol ® T-250) (Cι 8 -C 22 ) fatty alcohol polyglycol ethers with 25 EO units and / or iso- (Ci 6 -Cι 8 ) fatty alcohol polyglycol ethers with 25 EO units.
Bei den Genapol®-Typen handelt es sich um Produkte der Firma Clariant, GmbH.The Genapol ® types are products from Clariant, GmbH.
Bevorzugt beträgt das Molekulargewicht der Makromonomeren F) 200 g/mol bis 106 g/mol, besonders bevorzugt 150 bis 104 g/mol und insbesondere bevorzugt 200 bis 5000 g/mol.The molecular weight of the macromonomers F) is preferably 200 g / mol to 10 6 g / mol, particularly preferably 150 to 10 4 g / mol and particularly preferably 200 to 5000 g / mol.
Bezogen auf die Gesamtmasse der Copolymere können geeignete Makromonomere bis zu 99,8 Gew.-% eingesetzt werden. Bevorzugt finden die Bereiche 0,5 bis 30 Gew.-% und 70 bis 99,5 Gew.-% Anwendung. Besonders bevorzugt sind Anteile von 1 bis 20 Gew.-% und 75 bis 95 Gew.-%.Based on the total mass of the copolymers, suitable macromonomers up to 99.8% by weight can be used. The ranges 0.5 to 30% by weight and 70 to 99.5% by weight are preferably used. Fractions of 1 to 20% by weight and 75 to 95% by weight are particularly preferred.
Bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der der Komponenten A), C) und D) erhältlich sind.Preferred copolymers are those which can be obtained by copolymerizing at least that of components A), C) and D).
Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A), C) und E) erhältlich sind.Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), C) and E).
Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A), D) und F) erhältlich sind.Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), D) and F).
Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A) und F) erhältlich sind.Also preferred as copolymers are those which can be obtained by copolymerizing at least components A) and F).
Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A) und D) erhältlich sind.Also preferred as copolymers are those which can be obtained by copolymerizing at least components A) and D).
In einer bevorzugten Ausführungsform wird die Copolymerisation in Gegenwart mindestens eines polymeren Additivs G) durchgeführt, wobei das Additiv G) vor der eigentlichen Copolymerisation dem Polymerisationsmedium ganz- oder teilweise gelöst zugegeben wird. Die Verwendung von mehreren Additiven G) ist ebenfalls erfindungsgemäß. Vernetzte Additive G) können ebenfalls verwendet werden. Die Additive G) bzw. deren Mischungen müssen lediglich ganz oder teilweise im gewählten Polymerisationsmedium löslich sein. Während des eigentlichen Polymerisationsschrittes hat das Additiv G) mehrere Funktionen. Einerseits verhindert es im eigentlichen Polymerisationsschritt die Bildung übervernetzter Polymeranteile im sich bildenden Copolymerisat und andererseits wird das Additiv G) gemäß dem allgemein bekannten Mechanismus der Pfropf-Copolymerisation statistisch von aktiven Radikalen angegriffen. Dies führt dazu, dass je nach Additiv G) mehr oder weniger große Anteile davon in die Copolymere eingebaut werden. Zudem besitzen geeignete Additive G) die Eigenschaft, die Lösungsparameter der sich bildenden Copolymere während der radikalischen Polymerisationsreaktion derart zu verändern, dass die mittleren Molekulargewichte zu höheren Werten verschoben werden. Verglichen mit analogen Copolymeren, die ohne den Zusatz der Additive G) hergestellt wurden, zeigen solche, die unter Zusatz von Additiven G) hergestellt wurden, vorteilhafterweise eine signifikant höhere Viskosität in wässriger Lösung. Bevorzugt als Additive G) sind in Wasser und/oder Alkoholen, bevorzugt in t- Butanol, lösliche Homo- und Copolymere. Unter Copolymeren sind dabei auch solche mit mehr als zwei verschiedenen Monomertypen zu verstehen. Besonders bevorzugt als Additive G) sind Homo- und Copolymere aus N-Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon, Ethylenoxid, Propylenoxid, Acryloyldimethyltaurinsäure, N-Vinylcaprolactam, N-Vinylmethylacetamid, Acrylamid, Acrylsäure, Methacrylsäure, N-Vinylmorpholid, Hydroxyethylmethacrylat, Diallyldimethylammoniumchlorid (DADMAC) und/oder [2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC); Polyalkylenglykole und/oder Alkylpolyglykole. Insbesondere bevorzugt als Additive G) sind Polyvinylpyrrolidone (z.B. Luviskol K15®, K20®und K30® von BASF), Poly(N-Vinylformamide), Poly(N- Vinylcaprolactame) und Copolymere aus N-Vinylpyrrolidon, N-Vinylformamid und/oder Acrylsäure, die auch teilweise oder vollständig verseift sein können. Das Molekulargewicht der Additive G) beträgt bevorzugt 102 bis 107 g/mol, besonders bevorzugt 0,5*104 bis 106 g/mol.In a preferred embodiment, the copolymerization is carried out in the presence of at least one polymeric additive G), the additive G) before the actual copolymerization is added to the polymerization medium in whole or in part in solution. The use of several additives G) is also according to the invention. Crosslinked additives G) can also be used. The additives G) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium. During the actual polymerization step, additive G) has several functions. On the one hand, it prevents the formation of over-crosslinked polymer fractions in the copolymer being formed in the actual polymerization step and, on the other hand, additive G) is statistically attacked by active radicals in accordance with the generally known mechanism of graft copolymerization. As a result, depending on the additive G), more or less large amounts of it are incorporated into the copolymers. In addition, suitable additives G) have the property of changing the solution parameters of the copolymers which form during the radical polymerization reaction in such a way that the average molecular weights are shifted to higher values. Compared with analog copolymers which were produced without the addition of additives G), those which were produced with the addition of additives G) advantageously show a significantly higher viscosity in aqueous solution. Preferred additives G) are homo- and copolymers soluble in water and / or alcohols, preferably in t-butanol. Copolymers are also to be understood as meaning those with more than two different types of monomers. Particularly preferred additives G) are homopolymers and copolymers of N-vinylformamide, N-vinyl acetamide, N-vinyl pyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N-vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols. Particularly preferred additives G) are polyvinylpyrrolidones (such as Luviskol K15 ®, K20 ® and K30 ® from BASF), poly (N-vinylformamides), poly (N-vinylcaprolactams) and copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified. The molecular weight of the additives G) is preferably 10 2 to 10 7 g / mol, particularly preferably 0.5 * 10 4 to 10 6 g / mol.
Die Einsatzmenge des polymeren Additivs G) beträgt, bezogen auf die Gesamtmasse der bei der Copolymerisation zu polymerisierenden Monomere, bevorzugt 0,1 bis 90 Gew.-%, besonders bevorzugt 1 bis 20 Gew.-% und insbesondere bevorzugt 1 ,5 bis 10 Gew.-%.The amount of polymeric additive G) used is, based on the total mass of the monomers to be polymerized during the copolymerization, preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight .-%.
In einer weiteren bevorzugten Ausführungsform sind die erfindungsgemäßen Copolymere vernetzt, d.h. sie enthalten Comonomere mit mindestens zwei polymerisationsfähigen Vinylgruppen.In a further preferred embodiment, the copolymers according to the invention are crosslinked, i.e. they contain comonomers with at least two polymerizable vinyl groups.
Bevorzugte Vernetzer sind Methylenbisacrylamid; Methylenbismethacrylamid; Ester ungesättigter Mono- und Polycarbonsäuren mit Polyolen, bevorzugt Diacrylate und Triacrylate bzw. -methacrylate, besonders bevorzugt Butandiol- und Ethylenglykoldiacrylat bzw. -methacrylat, Trimethylolpropantriacrylat (TMPTA) und Trimethylolpropantrimethacrylat (TMPTMA); Allylverbindungen, bevorzugt Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraallyloxyethan, Triallylamin, Tetraallylethylendiamin; Allylester der Phosphorsäure; und/oder Vinylphosphonsäurederivate. Insbesondere bevorzugt als Vernetzer ist Trimethylolpropantriacrylat (TMPTA).Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives. Trimethylolpropane triacrylate (TMPTA) is particularly preferred as the crosslinking agent.
Der Gewichtsanteil an vernetzenden Comonomeren, bezogen auf die Gesamtmasse der Copolymere, beträgt bevorzugt bis 20 Gew.-%, besonders bevorzugt 0,05 bis 10 Gew.-% und insbesondere bevorzugt 0,1 bis 7 Gew.-%.The proportion by weight of crosslinking comonomers, based on the total mass of the copolymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.
Als Polymerisationsmedium können alle organischen oder anorganischen Lösungsmittel dienen, die sich bezüglich radikalischer Polymerisationsreaktionen weitestgehend inert verhalten und vorteilhafterweise die Bildung mittlerer oder hoher Molekulargewichte zulassen. Bevorzugt Verwendung finden Wasser; niedere Alkohole; bevorzugt Methanol, Ethanol, Propanole, iso-, sec- und t-Butanol, insbesondere bevorzugt t-Butanol; Kohlenwasserstoffe mit 1 bis 30 Kohlenstoffatomen und Mischungen der vorgenannten Verbindungen. Die Polymerisationsreaktion erfolgt bevorzugt im Temperaturbereich zwischen 0 und 150°C, besonders bevorzugt zwischen 10 und 100°C, sowohl bei Normaldruck als auch unter erhöhtem oder erniedrigtem Druck. Gegebenenfalls kann die Polymerisation auch unter einer Schutzgasatmosphäre, vorzugsweise unter Stickstoff, ausgeführt werden.All organic or inorganic solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which advantageously permit the formation of medium or high molecular weights. Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol; Hydrocarbons with 1 to 30 carbon atoms and mixtures of the aforementioned compounds. The polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C., particularly preferably between 10 and 100 ° C., both under normal pressure and under elevated or reduced pressure. If necessary, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.
Zur Auslösung der Polymerisation können energiereiche elektromagnetische Strahlen, mechanische Energie oder die üblichen chemischen Polymerisationsinitiatoren, wie organische Peroxide, z.B. Benzoylperoxid, tert.-Butylhydroperoxid, Methylethylketonperoxid, Cumolhydroperoxid, Dilauroylperoxid oder Azoinitiatoren, wie z.B. Azodiisobutyronitril (AIBN), verwendet werden. Ebenfalls geeignet sind anorganische Peroxyverbindungen, wie z.B. (NH )2S2O8, K2S2O8 oder H2O2, gegebenenfalls in Kombination mit Reduktionsmitteln (z.B. Natriumhydrogensulfit, Ascorbinsäure, Eisen(ll)-sulfat etc.) oder Redoxsystemen, welche als reduzierende Komponente eine aliphatische oder aromatische Sulfonsäure (z.B. Benzolsulfonsäure, Toluolsulfonsäure etc.) enthalten. Als Polymerisationsmedium können alle Lösungsmittel dienen, die sich bezüglich radikalischer Polymerisationsreaktionen weitestgehend inert verhalten und die Bildung hoher Molekulargewichte zulassen. Bevorzugt Verwendung finden Wasser und niedere, tertiäre Alkohole oder Kohlenwasserstoffe mit 3 bis 30 C-Atomen. In einer besonders bevorzugten Ausführungsweise wird t-Butanol als Reaktionsmedium verwendet. Mischungen aus zwei- oder mehreren Vertretern der beschriebenen potentiellen Lösungsmitteln sind selbstverständlich ebenfalls erfindungsgemäß. Dies schließt auch Emulsionen von nicht miteinander mischbaren Solventien ein (z.B. Wasser/Kohlenwasserstoffe). Grundsätzlich sind alle Arten der Reaktionsführung geeignet, die zu den erfindungsgemäßen Polymerstrukturen führen (Lösungspolymerisation, Emulsionsverfahren, Fällungsverfahren, Hochdruckverfahren, Suspensionsverfahren, Substanzpolymerisation, Gelpolymerisation usw.).High-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators, such as organic peroxides, for example benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as azodiisobutyronitrile (AIBN), can be used to initiate the polymerization. Also suitable are inorganic peroxy compounds, such as (NH) 2 S 2 O 8 , K 2 S 2 O 8 or H 2 O 2 , optionally in combination with reducing agents (for example sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or Redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component. All solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which permit the formation of high molecular weights. Water and lower, tertiary alcohols or hydrocarbons having 3 to 30 carbon atoms are preferably used. In a particularly preferred embodiment, t-butanol is used as the reaction medium. Mixtures of two or more representatives of the potential solvents described are of course also in accordance with the invention. This also includes emulsions of immiscible solvents (e.g. water / hydrocarbons). In principle, all types of reaction control which lead to the polymer structures according to the invention are suitable (solution polymerization, emulsion process, precipitation process, high-pressure process, suspension process, bulk polymerization, gel polymerization, etc.).
Bevorzugt eignet sich die Fällungspolymerisation, besonders bevorzugt die Fällungspolymerisation in tert.-Butanol. Die nachfolgende Auflistung zeigt 67 Copolymere, die für die Formulierung der erfindungsgemäßen Mittel besonders geeignet sind. Die verschiedenen Copolymere Nr. 1 bis Nr. 67 sind gemäß den folgenden Herstellverfahren 1 , 2, 3 und 4 erhältlich.Precipitation polymerization is particularly suitable, particularly preferably precipitation polymerization in tert-butanol. The following list shows 67 copolymers which are particularly suitable for the formulation of the agents according to the invention. The various copolymers No. 1 to No. 67 can be obtained according to the following production processes 1, 2, 3 and 4.
Verfahren 1 :Procedure 1:
Diese Polymere sind nach dem Fällungsverfahren in teil. Butanol herstellbar. Dabei wurden die Monomere in t-Butanol vorgelegt, die Reaktionsmischung inertisiert und anschließend die Reaktion nach Anheizen auf 60°C durch Zugabe des entsprechenden t-Butanol löslichen Initiators (bevorzugt Dilauroylperoxid) gestartet. Die Polymere werden nach beendeter Reaktion (2 Stunden) durch Absaugen des Lösungsmittels und durch anschließende Vakuumtrocknung isoliert.These polymers are in part after the precipitation process. Butanol can be produced. The monomers were initially introduced into t-butanol, the reaction mixture was rendered inert, and the reaction was then started after heating to 60 ° C. by adding the corresponding t-butanol-soluble initiator (preferably dilauroyl peroxide). After the reaction has ended (2 hours), the polymers are isolated by suction removal of the solvent and subsequent vacuum drying.
Verfahren 2: Diese Polymere sind nach dem Gelpolymerisationsverfahren in Wasser herstellbar. Dabei werden die Monomere in Wasser gelöst, die Reaktionsmischung inertisiert und anschließend die Reaktion nach Anheizen auf 65°C durch Zugabe von geeigneten Initiatoren- oder Initiatorsystemen (bevorzugt Na2S2θ8) gestartet. Die Polymergele werden anschließend zerkleinert und nach Trocknung die Polymere isoliert.Process 2: These polymers can be prepared in water using the gel polymerization process. The monomers are dissolved in water, the reaction mixture is rendered inert, and the reaction is then started after heating to 65 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 θ 8 ). The polymer gels are then crushed and the polymers isolated after drying.
Verfahren 3:Procedure 3:
Diese Polymere sind nach dem Emulsionsverfahren in Wasser herstellbar. Dabei werden die Monomere in einer Mischung aus Wasser/organ. Lösungsmittel (bevorzugt Cyclohexan) unter Verwendung eines Emulgators emulgiert, die Reaktionsmischung mittels N2 inertisiert und anschließend die Reaktion nach Anheizen auf 80°C durch Zugabe von geeigneten Initiatoren- oder Initiatorsystemen (bevorzugt Na2S2θ8) gestartet. Die Polymeremulsionen werden anschließend eingedampft (Cyclohexan fungiert als Schlepper für Wasser) und dadurch die Polymere isoliert.These polymers can be prepared in water using the emulsion process. The monomers are mixed in a water / organ mixture. Solvent (preferably cyclohexane) is emulsified using an emulsifier, the reaction mixture is rendered inert using N 2 and the reaction is then started after heating to 80 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 θ 8 ). The polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.
Verfahren 4:Procedure 4:
Diese Polymere sind nach dem Lösungsverfahren in organischen Lösungsmitteln (bevorzugt Toluol, z.B. auch teil. Alkohole) herstellbar. Dabei werden die Monomere im Lösungsmittel vorgelegt, die Reaktionsmischung inertisiert und anschließend die Reaktion nach Anheizen~äuf 70°C durch Zugabe von geeigneten Initiatoren- oder Initiatorsystemen (bevorzugt Dilauroylperoxid) gestartet. Die Polymere werden durch Abdampfen des Lösungsmittels und durch anschließende Vakuumtrocknung isoliert.These polymers are after the solution process in organic solvents (preferably toluene, for example also partially alcohols) can be prepared. The monomers (preferably dilauroyl peroxide) are initially charged in the solvent, the reaction mixture is rendered inert and then the reaction after initial heating äuf ~ 70 ° C by the addition of suitable initiators or initiator systems started. The polymers are isolated by evaporation of the solvent and subsequent vacuum drying.
Polymere mit hydrophoben Seitenketten, unvernetztPolymers with hydrophobic side chains, uncrosslinked
Polymere mit hydrophoben Seitenketten, vernetztPolymers with hydrophobic side chains, cross-linked
Polymere mit hydrophoben Seitenketten, vernetzt, gepfropftPolymers with hydrophobic side chains, cross-linked, grafted
Polymere mit siliziumhaltigen Gruppen, unvernetztPolymers with silicon-containing groups, uncrosslinked
Polymere mit siliziumhaltigen Gruppen, vernetztPolymers with silicon-containing groups, cross-linked
Polymere mit hydrophoben Seitenketten und kationischen Gruppen, unvernetztPolymers with hydrophobic side chains and cationic groups, uncrosslinked
Polymere mit hydrophoben Seitenketten und kationischen Gruppen, vernetztPolymers with hydrophobic side chains and cationic groups, cross-linked
Polymere mit fluorhaltigen GruppenPolymers with fluorine-containing groups
Multifunktionelle Polymere Multifunctional polymers
Chemische Bezeichnung der Reaktanden:Chemical name of the reactants:
AMPS Acryloyldimethyltaurat, wahlweise Na- oder NH4-SalzAMPS Acryloyldimethyltaurate, optionally Na or NH4 salt
Genapol® T-080 Ci6-Cι8-Fettalkoholpolyglykolether mit 8 EO-Einheiten Genapol® T-110 Cι2-Cι -Fettalkoholpolyglykolether mit 11 EO-Einheiten Genapol® T-250 Ci6-Cιs-Fettalkoholpolyglycolether mit 25 EO-EinheitenGenapol ® T-080 Ci 6 -Cι 8 fatty alcohol polyglycol ether with 8 EO units Genapol ® T-110 Cι 2 -Cι fatty alcohol polyglycol ether with 11 EO units Genapol ® T-250 Ci 6 -Cιs fatty alcohol polyglycol ether with 25 EO units
Genapol® LA-040 C12-C14-Fettalkoholpolyglykolether mit 4 EO-Einheiten Genapol® LA-070 C12-Cι -Fettalkoholpolyglykolether mit 7 EO-Einheiten Genapol® O-150 methacrylat Cι6-C18-Fettalkoholpolyglykolether methacrylat mit 15 EO-Einheiten,Genapol ® LA-040 C 12 -C 14 fatty alcohol polyglycol ether with 4 EO units Genapol ® LA-070 C 12 -Cι fatty alcohol polyglycol ether with 7 EO units Genapol ® O-150 methacrylate Cι 6 -C 18 fatty alcohol polyglycol ether methacrylate with 15 EO -Units,
Genapol® LA-250 crotonat Ci2-C1 -Fettalkoholpolyglykolether crotonat mitGenapol ® LA-250 crotonat Ci 2 -C 1 fatty alcohol polyglycol ether crotonat with
25 EO-Einheiten25 EO units
Genapol® T-250 methacrylat Ci6-Cι8-Fettalkoholpolyglycolether methacrylat mit 25 EO-EinheitenGenapol ® T-250 methacrylate Ci 6 -Cι 8 fatty alcohol polyglycol ether methacrylate with 25 EO units
Genapol® T-250 acrylat Ci6-C18-Fettalkoholpolyglycolether methacrylat mit 25 EO-EinheitenGenapol ® T-250 acrylate Ci 6 -C 18 fatty alcohol polyglycol ether methacrylate with 25 EO units
BB10® Polyoxyethylen(10)Behenylether TMPTA Trimethylolpropantriacrylat Poly-NVP Poly-N-Vinylpyrrolidon Silvet® 867 Siloxan Polyalkylenoxid Copolymer MBA Methylen-bis-acrylamid AMA AllylmethacrylatBB10 ® polyoxyethylene (10) behenyl ether TMPTA trimethylolpropane triacrylate poly-NVP poly-N-vinylpyrrolidone Silvet ® 867 siloxane polyalkylene oxide copolymer MBA methylene-bis-acrylamide AMA allyl methacrylate
®Y-12867 Siloxan Polyalkylenoxid Copolymer ® Y-12867 siloxane polyalkylene oxide copolymer
Silvet® 7608 Polyalkylenoxid-modifiziertesSilvet ® 7608 polyalkylene oxide modified
Heptamethyltrisiloxan Silvet® 7280 Polyalkylenoxid-modifiziertesHeptamethyltrisiloxane Silvet ® 7280 polyalkylene oxide modified
Heptamethyltrisiloxanheptamethyltrisiloxane
DADMAC Diallyldimethyl-ammoniumchloridDADMAC diallyldimethyl ammonium chloride
HEMA 2-HydroxyethylmethacrylatHEMA 2-hydroxyethyl methacrylate
Quat 2-(Methacryloyloxy)ethyltrimethylammoniumchlorid Fluowet® AC 600 PerfluoralkylethylacrylatQuat 2- (methacryloyloxy) ethyl trimethyl ammonium chloride FLUOWET® ® AC 600 perfluoroalkylethyl
Span® 80 SorbitanesterSpan ® 80 sorbitan esters
In einer bevorzugten Ausführungsform sind die Copolymere wasserlöslich oder wasserquellbar.In a preferred embodiment, the copolymers are water-soluble or water-swellable.
Die beschriebene, optional durchführbare Pfropfung der Copolymere mit anderen Polymeren führt zu Produkten mit besonderer Polymermorphologie, die in wässrigen Systemen optisch klare Gele ergeben. Ein potenzieller Nachteil der Copolymere ohne Pfropfung besteht in einer mehr oder weniger starken Opaleszenz in wässriger Lösung. Diese beruht auf bisher nicht zu vermeidenden, übervernetzten Polymeranteilen, die während der Synthese entstehen und in Wasser nur unzureichend gequollen vorliegen. Dadurch bilden sich Licht streuende Teilchen aus, deren Größe deutlich oberhalb der Wellenlänge des sichtbaren Lichts liegt und deshalb Ursache der Opaleszenz sind. Durch das beschriebene, optional durchführbare Pfropfverfahren wird die Bildung übervernetzterThe described, optionally feasible grafting of the copolymers with other polymers leads to products with a particular polymer morphology which result in optically clear gels in aqueous systems. A potential disadvantage of the copolymers without grafting is a more or less strong opalescence in aqueous solution. This is based on previously unavoidable, over-crosslinked polymer fractions that arise during the synthesis and are not sufficiently swollen in water. As a result, light-scattering particles form, the size of which is well above the wavelength of visible light and are therefore the cause of opalescence. The described, optionally feasible grafting process makes the formation of cross-linked
Polymeranteile gegenüber herkömmlichen Techniken deutlich reduziert oder gänzlich vermieden.Polymer content significantly reduced or completely avoided compared to conventional techniques.
Die beschriebene, optional durchführbare Inkorporation sowohl von kationischen Ladungen als auch von Silizium-, Fluor oder Phosphoratomen in die Copolymere führt zu Produkten, die in kosmetischen Formulierungen besondere sensorische und Theologische Eigenschaften besitzen. Eine Verbesserung der sensorischen und rheologischen Eigenschaften kann insbesondere bei der Verwendung in Rinse-off Produkten vorteilhaft sein.The described, optionally feasible incorporation of both cationic charges and silicon, fluorine or phosphorus atoms into the copolymers leads to products which have special sensory and theological properties in cosmetic formulations. An improvement in sensory and rheological properties can be particularly advantageous when used in rinse-off products.
Siliziummodifizierte Copolymere können die Funktionen von Silikonölen in teilweise oder in vollem Umfang übernehmen. Der Einsatz von Silikonen kann durch die Copolymere reduziert oder vermieden werden.Silicon-modified copolymers can take over the functions of silicone oils in part or in full. The copolymers can reduce or avoid the use of silicones.
Die erfindungsgemäßen Deodorantien und Antiperspirantien enthalten, bezogen auf die fertigen Mittel, bevorzugt 0,01 bis 10 Gew.-%, besonders bevorzugt 0,1 bis 5 Gew.-%, insbesondere bevorzugt 0,5 bis 3 Gew.-% der Copolymere.The deodorants and antiperspirants according to the invention contain, based on the finished compositions, preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight of the copolymers.
Bevorzugt enthalten die erfindungsgemäßen Mittel 0,01 bis 89 Gew.-%, besonders bevorzugt 5 bis 50 Gew.-%, insbesondere bevorzugt 10 bis 30 Gew.-% Wasser.The agents according to the invention preferably contain 0.01 to 89% by weight, particularly preferably 5 to 50% by weight, particularly preferably 10 to 30% by weight of water.
Bevorzugt enthalten die erfindungsgemäßen Mittel bis 10 Gew.-%, bevorzugt 1 bis 6 Gew.-% Glycerin.The agents according to the invention preferably contain up to 10% by weight, preferably 1 to 6% by weight, of glycerol.
Bevorzugt enthalten die erfindungsgemäßen Mittel antimikrobielle Wirkstoffe, die die schweißzersetzenden Mikroorganismen bzw. das schweißzersetzende Esterase-Enzym hemmen. Bevorzugt geeignet als antimikrobielle Wirkstoffe sindThe agents according to the invention preferably contain antimicrobial active substances which inhibit the sweat-decomposing microorganisms or the sweat-decomposing esterase enzyme. Are preferably suitable as antimicrobial agents
Cetyltrimethylammoniumchlorid, Cetylpyridiniumchlorid, Benzethoniumchlorid, Diisobutylethoxyethyldimethylbenzylammoniumchlorid, Natrium N-Laurylsarcosinat, Natrium-N-Palmethylsarcosinat, Lauroylsarcosin, N-Myristoylglycin, Kalium-N- Laurylsarcosin, Trimethylammoniumchlorid, Natriumaluminiumchlorohydroxylactat, Triethylcitrat, Tricetylmethylammoniumchlorid, 2,4,4,-Trichloro-2'-hydroxy- diphenylether (Triclosan), Phenoxyethanol, 1,5-Pentandiol, 1 ,6-Hexandiol, 3,4,4'-tr.chlorocarbani!id (Triclocarban), Diaminoalkylamid, beispielsweise L-Lysinhexadecylamid, Citratschwermetallsalze, Salicylate, Piroctose, insbesondere Zinksalze, Pyrithione und deren Schwermetallsalze, insbesondere Zinkpyrithion, Zinkphenolsulfa, Famesol und Kombinationen dieser Wirksubstanzen. Die erfindungsgemäßen Mittel enthalten die antimikrobiellen Mittel bevorzugt in Mengen bis 50 Gew.-%, besonders bevorzugt 0,01 bis 10 Gew.-%, insbesondere bevorzugt 0,1 bis 10 Gew.-%.Cetyltrimethylammonium chloride, cetylpyridinium chloride, benzethonium chloride, Diisobutylethoxyethyldimethylbenzylammoniumchlorid, sodium N-lauryl sarcosinate, sodium N-Palmethylsarcosinat, lauroyl sarcosine, N-myristoyl glycine, potassium N-lauryl sarcosine-, trimethylammonium chloride, Natriumaluminiumchlorohydroxylactat, triethyl citrate, tricetylmethyl ammonium chloride, 2,4,4 -Trichloro-2 ' -hydroxy-diphenyl ether (triclosan), phenoxyethanol, 1,5-pentanediol, 1,6-hexanediol, 3,4,4'-tr.chlorocarbani! id (triclocarban), diaminoalkylamide, for example L-lysine hexadecylamide, citrate heavy metal salts, salicylates, piroctose , in particular zinc salts, pyrithione and their heavy metal salts, in particular zinc pyrithione, zinc phenol sulfa, famesol and combinations of these active substances. The agents according to the invention preferably contain the antimicrobial agents in amounts of up to 50% by weight, particularly preferably 0.01 to 10% by weight, particularly preferably 0.1 to 10% by weight.
Bevorzugt enthalten die erfindungsgemäßen Mittel Adstringenzien.The agents according to the invention preferably contain astringents.
Bevorzugte Adstringenzien sind Oxide, bevorzugt Magnesiumoxid, Aluminiumoxid, Titandioxid, Zirkondioxid und Zinkoxid, Oxidhydrate, bevorzugt Aluminiumoxidhydrat (Böhmit) und Hydroxide, bevorzug von Calcium, Magnesium, Aluminium, Titan, Zirkon oder Zink. Die erfindungsgemäßen Mittel enthalten die adstringenden Wirkstoffe bevorzugt in Mengen 0 bis 50 Gew.-%, besonders bevorzugt 0,01 bis 10 Gew.-% und insbesondere bevorzugt 0,1 bis 10 Gew.-%.Preferred astringents are oxides, preferably magnesium oxide, aluminum oxide, titanium dioxide, zirconium dioxide and zinc oxide, oxide hydrates, preferably aluminum oxide hydrate (boehmite) and hydroxides, preferably calcium, magnesium, aluminum, titanium, zirconium or zinc. The agents according to the invention preferably contain the astringent active ingredients in amounts of 0 to 50% by weight, particularly preferably 0.01 to 10% by weight and particularly preferably 0.1 to 10% by weight.
Weiterhin bevorzugt enthalten die erfindungsgemäßen Mittel Gelierungsmittel. Als Gelierungsmittel eignen sich alle oberflächenaktiven Stoffe, die in der flüssigen Phase gelöst eine Netzwerkstruktur ausbilden und so die flüssige Phase verfestigen.The agents according to the invention further preferably contain gelling agents. Suitable gelling agents are all surface-active substances which, when dissolved in the liquid phase, form a network structure and thus solidify the liquid phase.
Geeignete Geliermittel sind z.B. in WO 98/58625 genannt.Suitable gelling agents are e.g. mentioned in WO 98/58625.
Bevorzugte Gelierungsmittel sind Metallsalze von Fettsäuren, bevorzugt mit 12 bis 22 C-Atomen, beispielsweise Natriumstearat, Natriumpalmitat, Natriumlaurat, Natriumarachidate, Natriumbehenat, Kaliumstearat, Kaliumpalmitat, Natriummyristat, Kaliumpalmitat, Aluminiummonostearat, Hydroxyfettsäuren, beispielsweise 12-Hydroxystearinsäure, -lauryl-, 16-Hydroxyhexadecanoylsäure; Fettsäureamide; Fettsäurealkanolamide; Dibenzalsorbit und alkohollösliche Polyamide und Polyacrylamide oder Mischungen solcher.Preferred gelling agents are metal salts of fatty acids, preferably with 12 to 22 carbon atoms, for example sodium stearate, sodium palmitate, sodium laurate, sodium arachidates, sodium behenate, potassium stearate, potassium palmitate, sodium myristate, potassium palmitate, aluminum monostearate, hydroxy fatty acids, for example 12-hydroxystearic acid, 16-lauryl acid, 16-lauryl acid, Hydroxyhexadecanoylsäure; fatty acid amides; fatty acid; Dibenzalsorbit and alcohol-soluble polyamides and polyacrylamides or mixtures thereof.
Bevorzugt enthalten die erfindungsgemäßen Mittel 0,01 bis 20 Gew.-%, besonders bevorzugt 0,1 bis 10 Gew.-%, insbesondere bevorzugt 1 bis 8 Gew.-% und ganz besonders bevorzugt 3 bis 7 Gew.-% an Geliermitteln. In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Mittel zusätzliche Alkohole.The agents according to the invention preferably contain 0.01 to 20% by weight, particularly preferably 0.1 to 10% by weight, particularly preferably 1 to 8% by weight and very particularly preferably 3 to 7% by weight of gelling agents. In a further preferred embodiment, the agents according to the invention contain additional alcohols.
Bevorzugte Alkohole sind alkoxylierte Alkohole mit bevorzugt 1 bis 80, besonders bevorzugt 3 bis 20, Alkoxygruppen und mindestens einer freien Hydroxylgruppe. Besonders bevorzugt sind Ethanol, Propanol, Isopropanol, n-Butanol, i-Butanol, t-Butanol, Glycerin, Diethylenglykol, Triethylenglykol, Dipropylenglykol, Tripropylenglykol, flüssige Polypropylenpolyethylenglycol-Copolymere, Tetrapropylenglykol, Tetraethylenglykol, Dibutylenglykol, Trimethylenglykol, Diethylenglycolmonoethylether, PEG-8, 1 ,3-Butandiol, 1 ,4-Butandiol, Glycerolpropoxylat, Propylenglycol, Hexylenglykol, 1 ,2-Hexandiol, 1 ,3-Butylenglycol, 1 ,2,6-Trihydroxyhexan und 1 , 2, 3-Trihydroxhexan. Weitere bevorzugte Alkohole sind Polyethylenglykole mit einer relativen Molekülmasse unter 2000. Insbesondere ist ein Einsatz von Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 600 und in Mengen bis zu 45 Gew.-% und von Polyethylenglykol mit einer relativen Molekülmasse zwischen 400 und 600 in Mengen von 5 bis 25 Gew.-% bevorzugt.Preferred alcohols are alkoxylated alcohols with preferably 1 to 80, particularly preferably 3 to 20, alkoxy groups and at least one free hydroxyl group. Ethanol, propanol, isopropanol, n-butanol, i-butanol, t-butanol, glycerin, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, liquid polypropylene polyethylene glycol copolymers, tetrapropylene glycol, tetraethylene glycol, dibutylene glycol, 8-ethylene glycol, trimethylene glycol, trimethylene glycol, trimethylene glycol, trimethylene glycol, particularly preferred are 1, 3-butanediol, 1, 4-butanediol, glycerol propoxylate, propylene glycol, hexylene glycol, 1, 2-hexanediol, 1, 3-butylene glycol, 1, 2,6-trihydroxyhexane and 1, 2, 3-trihydroxhexane. Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000. In particular, use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred.
Die erfindungsgemäßen Mittel enthalten bevorzugt 5 bis 90 Gew.-%, besonders bevorzugt 5 bis 80 Gew.-% und insbesondere bevorzugt 20 bis 60 Gew.-% an Alkohol.The agents according to the invention preferably contain 5 to 90% by weight, particularly preferably 5 to 80% by weight and particularly preferably 20 to 60% by weight of alcohol.
Als Duft- bzw. Parfümöle können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethyl-methylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8 bis 18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cycllamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die lonone, alpha- Isomethylionon und Methyl-cedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geranion, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene und Balsame. Bevorzugt werden Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen.Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as fragrance or perfume oils. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropylate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cycllamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the ionones, alpha-isomethyl ionone and methyl cedryl ketone , to the alcohols anethole, citronellol, eugenol, geranion, linalool, phenylethyl alcohol and terpineol, to the Hydrocarbons mainly include the terpenes and balms. Mixtures of different fragrances are preferably used, which together produce an appealing fragrance.
Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen oder tierischen Quellen zugänglich sind, z.B. Pinien-, Citrus-, Jasmin-, Lilien-, Rosen-, oder Ylang-Ylang-Öl. Auch ätherische Öle geringerer Flüchtigkeit, die meist als Aromakomponenten verwendet werden, eignen sich als Parfümöle, z.B. Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzenöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeerenöl, Vetiveröl, Olibanöl, Galbanumöl und Ladanumöl.Perfume oils can also contain natural fragrance mixtures, such as are available from plant or animal sources, e.g. Pine, citrus, jasmine, lily, rose, or ylang-ylang oil. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil and ladanum oil.
Die erfindungsgemäßen Mittel können als weitere Hilfs- und Zusatzstoffe Olkörper, Emulgatoren und Co-Emulgatoren, Überfettungsmittel, feuchtigkeitsspendende Mittel, Stabilisatoren, biogene Wirkstoffe (Lokalanästhetika, Antibiotika,The agents according to the invention can contain, as further auxiliaries and additives, oil bodies, emulsifiers and co-emulsifiers, superfatting agents, moisturizing agents, stabilizers, biogenic agents (local anesthetics, antibiotics,
Antiphlogistik, Antiallergica, Corticosteroide, Sebostatika), Vitamine, Phanthenol, Allantoin, Pflanzenextrakte, beispielsweise Aloe Vera und Proteine, Glycerin, Konservierungsmittel, Perlglanzmittel, Färb- und Duftstoffe, Lösungsmittel, Hydrotrope, Enzyme, Trägersubstanzen, beispielsweise Schichtsilikate, pyrogene Kieselsäure, Elektrolytsalze wie KCI, NaCI, Komplexbildner, Antioxidation und UV- Lichtschutzfilter enthalten.Antiphlogistics, antiallergics, corticosteroids, sebostatics), vitamins, phanthenol, allantoin, plant extracts, e.g. aloe vera and proteins, glycerin, preservatives, pearlescent agents, colorants and fragrances, solvents, hydrotropes, enzymes, carrier substances, e.g. layered silicates, pyrogenic silica such as electrolytes Contain KCI, NaCI, complexing agent, antioxidation and UV light protection filter.
Unter Olkörper ist jegliche Fettsubstanz zu verstehen, die bei Raumtemperatur (25°C) flüssig ist.Oil body means any fatty substance that is liquid at room temperature (25 ° C).
Die Fett-Phase kann ein oder mehrere Öle umfassen, die vorzugsweise aus folgenden Ölen ausgewählt werden:The fat phase can comprise one or more oils, which are preferably selected from the following oils:
a) Silikonöle, flüchtig oder nicht flüchtig, linear, verzweigt oder ringförmig, eventuell organisch modifiziert, Phenylsilikone, Silikonharze und -gummis, die bei Raumtemperatur fest oder flüssig sind: b) Mineralöle, wie Paraffin- oder Vaselinöl c) Öle tierischen Ursprungs, wie Perhydrosqualen oder Lanolin; d) Öle pflanzlichen Ursprungs, wie flüssige Triglyceride, z.B. Sonnenblumen-, Mais-, Soja-, Reis-, Jojoba-, Babusscu-, Kürbis-, Traubenkern-, Sesam-, Walnuss-, Aprikosen-, Makadamia-, Avocado-, Süßmandel-, Wiesenschaumkraut-, Ricinusöl, Triglyceride der Capryl/Caprinsäuren, Olivenöl, Erdnussöl, Rapsöl und Kokosnussöl; e) synthetische Öle, wie Purcellinöl, Isoparaffine, lineare und/oder verzweigte Fettalkohole und Fettsäureester, bevorzugt Guerbetalkohole mit 6 bis 18, vorzugsweise 8 bis 10, Kohlenstoffatomen; Ester von linearen (C6-Ci3)- Fettsäuren mit linearen (C6-C o)-Fettalkoholen; Ester von verzweigten (C6-Ci3)-Carbonsäuren mit linearen (C6-C2o)-Fettalkoholen, Ester von linearen (C6-Cι8)-Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol; Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z.B. Dimerdiol oder Trimerdiol) und/oder Guerbetalkoholen; Triglyceride auf Basis (C6-Cι0)-Fettsäuren, f) Ester, wie Dioctyladipat, Diisopropyl dimer dilineloat, Propylenglykole/- dicaprilat oder Wachse wie Bienenwachs, Paraffinwachs oder Mikrowachse, gegebenenfalls in Kombination mit hydrophilen Wachsen, wie z.B. Cetylstearylalkohol, g) fluorierte und perfluorierte Öle; h) fluorierte Silikonöle; i) Gemische der obengenannten Substanzen.a) Silicone oils, volatile or non-volatile, linear, branched or ring-shaped, possibly organically modified, phenyl silicones, silicone resins and rubbers which are solid or liquid at room temperature: b) mineral oils, such as paraffin or petroleum jelly oil c) oils of animal origin, such as Perhydrosqualene or lanolin; d) oils of vegetable origin, such as liquid triglycerides, for example sunflower, corn, soybean, rice, jojoba, babusscu, pumpkin, grape seed, sesame, walnut, apricot, macadamia, avocado, Sweet almond, cuckoo, castor oil, triglycerides of caprylic / capric acids, olive oil, peanut oil, rapeseed oil and coconut oil; e) synthetic oils, such as purcellin oil, isoparaffins, linear and / or branched fatty alcohols and fatty acid esters, preferably Guerbet alcohols having 6 to 18, preferably 8 to 10, carbon atoms; Esters of linear (C 6 -Ci 3 ) fatty acids with linear (C 6 -C o) fatty alcohols; Esters of branched (C 6 -C 3 ) carboxylic acids with linear (C 6 -C 2 o) fatty alcohols, esters of linear (C 6 -C 8 ) fatty acids with branched alcohols, especially 2-ethylhexanol; Esters of linear and / or branched fatty acids with polyhydric alcohols (such as dimer diol or trimer diol) and / or Guerbet alcohols; Triglycerides based on (C 6 -Cι 0 ) fatty acids, f) esters such as dioctyl adipate, diisopropyl dimer dilineloat, propylene glycols / dicaprilat or waxes such as beeswax, paraffin wax or microwaxes, optionally in combination with hydrophilic waxes, such as cetylstearyl alcohol, g) fluorinated and perfluorinated oils; h) fluorinated silicone oils; i) Mixtures of the above substances.
Als nichtionogene Co-Emulgatoren kommen u.a. in Betracht Anlagerungsprodukte von 0 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe und an Sorbitan- bzw. Sorbitolester; (Cι2-C18)-Fettsäuremono~ und -diester von Anlagerungsprodukten von 0 bis 30 Mol Ethylenoxid an Glycerin; Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und ggfs. deren Ethylenoxidanlagerungsprodukten; Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Rizinusöl und/oder gehärtetes Rizinusöl; Polyol- und insbesondere Polyglycerinester, wie z.B. Polyglycerinpolyricinoleat und Polyglycerinpoly-12-hydroxystearat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen.Suitable nonionic co-emulsifiers are, inter alia, addition products of 0 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and on sorbitan or sorbitol esters; (-C 2 -C 18 ) fatty acid monoesters and diesters of adducts of 0 to 30 mol of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and, if appropriate, their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters, such as Polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable.
Als ionogene Co-Emulgatoren eignen sich z.B. anionische Emulgatoren, wie mono-, di- oder tri-Phosphorsäureester, aber auch kationische Emulgatoren wie mono-, di- und tri-Alkylquats und deren polymere Derivate.Suitable ionogenic co-emulsifiers are e.g. anionic emulsifiers, such as mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers, such as mono-, di- and tri-alkyl quats and their polymeric derivatives.
Als Überfettungsmittel können Substanzen wie beispielsweise polyethoxylierte Lanolinderivate, Lecithinderivate, Polyolfettsäureester, Monoglyceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen. Als feuchtigkeitsspendende Substanz stehen beispielsweise Isopropylpalmitat, Glycerin und/ oder Sorbitol zu Verfügung.Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. For example, isopropyl palmitate, glycerin and / or sorbitol are available as a moisturizing substance.
Als Stabilisatoren können Metallsalze von Fettsäuren, wie z.B. Magnesium-, Aluminium- und/oder Zinkstearat eingesetzt werden.Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate can be used.
Unter biogenen Wirkstoffen sind beispielsweise Pflanzenextrakte und Vitaminkomplexe zu verstehen.Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.
Die erfindungsgemäßen Mittel können mit konventionellen Ceramiden, Pseudoceramiden, Fettsäure-N-alkylpolyhydroxyalkylamiden, Cholesterin, Cholesterinfettsäureestern, Fettsäuren, Triglyceriden, Cerebrosiden, Phospholipiden und ähnlichen Stoffen als Pflegezusatz abgemischt werden.The agents according to the invention can be mixed with conventional ceramides, pseudoceramides, fatty acid-N-alkylpolyhydroxyalkylamides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances as a care additive.
Um die rheologischen Eigenschaften von wässrigen oder lösungsmittelhaltigen Emulsionen oder Suspensionen einzustellen, werden in der Fachliteratur eineIn order to adjust the rheological properties of aqueous or solvent-based emulsions or suspensions, a
Vielzahl von unterschiedlichen Systemen angegeben. Bekannt sind beispielsweise Celluloseether und andere Cellulosederivate (z.B. Carboxymethylcellulose, Hydroxyethylcellulose), Gelatine, Stärke und Stärkederivate, Natriumalginate, Fettsäurepolyethylenglykolester, Agar-Agar, Traganth oder Dextrine. Als synthetische Polymere kommen verschiedene Materialien zum Einsatz, wie z.B. Polyvinylalkohole, Polyacrylamide, Polyvinylamide, Polysulfonsäuren, Polyacrylsäure, Polyacrylsäureester, Polyvinylpyrrolidon, Polyvinylmethylether, Polyethylenoxide, Copolymere aus Maleinsäureanhydrid und Vinylmethylether, sowie diverse Mischungen und Copolymerisate aus den o.a. Verbindungen, einschließlich ihrer verschiedenen Salze und Ester. Diese Polymere können wahlweise vernetzt oder unvernetzt sein.Variety of different systems specified. For example, cellulose ethers and other cellulose derivatives (eg carboxymethyl cellulose, hydroxyethyl cellulose), gelatin, starch and starch derivatives, sodium alginates, fatty acid polyethylene glycol esters, agar-agar, tragacanth or dextrins are known. Various materials are used as synthetic polymers, such as, for example, polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers of the above compounds, including their various salts and esters. These polymers can optionally be cross-linked or uncross-linked.
Als UV-Filter eignen sich z.B. 4-Aminobenzoesäure;Suitable UV filters are e.g. 4-aminobenzoic acid;
3-(4,-Trimethylammonium)benzyliden-boran-2-on-methylsulfat; 3,3,5-Trimethyl-cyclohexylsalicylat; 2-Hydroxy-4-methoxybenzophenon; 2-Phenylbenzimidazol-5-sulfonsäure und ihre Kalium-, Natrium- und Triethanolaminsalze; 3,3,-(1 ,4-Phenylendimethin)-bis-(7,7-dimethyl-2- oxobicyclo[2.2.1]-heptan-1-methansulfonsäure und ihre Salze; 1-(4-tert.-3- (4 , -trimethylammonium) benzylidene-boran-2-one methyl sulfate; 3,3,5-trimethyl-cyclohexyl salicylate; 2-hydroxy-4-methoxybenzophenone; 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts; 3,3 , - (1,4-phenylenedimethine) -bis- (7,7-dimethyl-2-oxobicyclo [2.2.1] -heptane-1-methanesulfonic acid and its salts; 1- (4-tert.-
Butylphenyl)-3-(4-methoxyphenyl)propan-1 ,3-dion, S-^-Sulft-O-benzyliden-boman- 2-on und seine Salze; 2-Cyan-3,3-diphenyl-acrylsäure-(2-ethylhexylester); Polymer von N-[2(und 4)-(2-oxoborn-3-ylidenmethyl)benzyl]-acrylamid; 4-Methoxy- zimtsäure-2-ethyl-hexylester; ethoxyliertes Ethyl-4-amino-benzoat; 4-Methoxy- zimtsäure-isoamylester; 2,4,6-Tris-[p-(2-ethylhexyloxycarbonyl)anilino]-1 ,3,5- triazin; 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1 ,3,3,3-tetramethyl-1- (trimethylsilyloxy)-disiloxanyl)propyl)phenol;Butylphenyl) -3- (4-methoxyphenyl) propan-1, 3-dione, S - ^ - Sulft-O-benzylideneboman-2-one and its salts; 2-cyano-3,3-diphenyl-acrylic acid (2-ethylhexyl); Polymer of N- [2 (and 4) - (2-oxoborn-3-ylidenemethyl) benzyl] acrylamide; 2-ethylhexyl 4-methoxycinnamate; ethoxylated ethyl 4-amino benzoate; 4-methoxy cinnamic acid isoamyl ester; 2,4,6-tris- [p- (2-ethylhexyloxycarbonyl) anilino] -1, 3,5-triazine; 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1, 3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol;
4,4,-[(6-[4-((1 ,1-dimethylethyl)-amino-carbonyl)phenylamino]-1 ,3,5-triazin-2,4- yl)diimino]bis-(benzoesäure-2-ethylhexylester); 3-(4Λ-Methylbenzyliden)-D,L-Campher; 3-BenzyIiden-Campher; Salicylsäure-2- ethylhexylester; 4-Dimethylaminobenzoesäure-2-ethylhexylester; Hydroxy-4- methoxy-benzophenon-5-sulfonsäure (Sulisobenzonum) und das Natriumsalz; und/oder 4-lsopropylbenzylsalicylat.4,4 , - [(6- [4 - ((1, 1-dimethylethyl) aminocarbonyl) phenylamino] -1, 3,5-triazin-2,4-yl) diimino] bis- (benzoic acid-2 -ethylhexylester); 3- (4 Λ- methylbenzylidene) -D, L-camphor; 3-BenzyIiden-camphor; 2-ethylhexyl salicylic acid; 4-dimethylaminobenzoic acid 2-ethylhexyl ester; Hydroxy-4-methoxy-benzophenone-5-sulfonic acid (Sulisobenzonum) and the sodium salt; and / or 4-isopropylbenzyl salicylate.
Als Antioxidantien stehen beispielsweise Superoxid-Dismutase, Tocopherol (Vitamin E) und Ascorbinsäure (Vitamin C) zur Verfügung.For example, superoxide dismutase, tocopherol (vitamin E) and ascorbic acid (vitamin C) are available as antioxidants.
Als Konservierungsmittel in Betracht kommen beispielsweise Phenoxyethanol, Parabene, Pentandiol oder Sorbinsäure.Examples of suitable preservatives are phenoxyethanol, parabens, pentanediol or sorbic acid.
Als Farbstoffe können die für kosmetische Zwecke geeigneten und zugelassenen Substanzen verwendet werden. Bevorzugt handelt es sich bei den Deodorantien und Antiperspirantien um Lotionen, Cremes, Stifte (auch Mehrphasenstifte), Sprays, Roll-On-Präparate und Puder.The dyes which can be used are those which are suitable and approved for cosmetic purposes. The deodorants and antiperspirants are preferably lotions, creams, pens (also multi-phase pens), sprays, roll-on preparations and powders.
Die erfindungsgemäßen Mittel haben bevorzugt einen pH-Wert von 2 bis 12, besonders bevorzugt von 3 bis 8.The agents according to the invention preferably have a pH of 2 to 12, particularly preferably 3 to 8.
Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung, ohne sie jedoch einzuschränken (bei allen Prozentangaben handelt es sich um Gew.-%). Bei den in den Beispielen verwendeten Copolymeren handelt es sich um Vertreter der in der Beschreibung bereits aufgeführten besonders bevorzugten Copolymere Nr.1 bis Nr.67. Die Herstellung erfolgte nach den dort angegebenen Verfahren 1 , 2, 3 oder 4 unter Verwendung der bevorzugten Initiatoren und Lösemittel.The following examples serve to illustrate the invention, but without restricting it (all percentages are% by weight). The copolymers used in the examples are representatives of the particularly preferred copolymers No. 1 to No. 67 already listed in the description. The preparation was carried out according to methods 1, 2, 3 or 4 given there using the preferred initiators and solvents.
Beispiel 1: Antiperspirant-CremeExample 1: Antiperspirant cream
A Cithrol GMS A/S 15,0 %A Cithrol GMS A / S 15.0%
Glyceryl Stearat/ PEG-100 StearatGlyceryl stearate / PEG-100 stearate
Crodacol C90 EP 5,0 %Crodacol C90 EP 5.0%
Cetylalkoholcetyl alcohol
Copolymer Nr. 61 2,0 %Copolymer No. 61 2.0%
B Wasser ad 100 %B water ad 100%
Sorbit (70 %ig) 3,0 %Sorbitol (70%) 3.0%
Sorbitolsorbitol
Reach 501 Lsg. 44,5 %Reach 501 solution 44.5%
Aluminium ChlorohydratAluminum chlorohydrate
Parfümöl q.s.Perfume oil q.s.
Farbstoffe q.s.Dyes q.s.
Duftstoffe q.s.Fragrances q.s.
Herstellung:production:
I A und B ohne Reach 501 auf 70 bis 75°C erhitzenHeat I A and B to 70 to 75 ° C without Reach 501
II Unter Rühren abkühlen lassenII Let cool while stirring
III Reach 501 bei 50 bis 55°C hinzufügen IV Parfümöl bei 40 bis 45°C hinzugebenIII Add Reach 501 at 50 to 55 ° C IV Add perfume oil at 40 to 45 ° C
V Bei 30 bis 35°C homogenisierenV Homogenize at 30 to 35 ° C
Beispiel 2: Klares Antiperspirant-GelExample 2: Clear antiperspirant gel
A Abil EM97 2,3 %A Abil EM97 2.3%
Dimethicon Copolyl/CyclopentasiloxanDimethicone copolyl / cyclopentasiloxane
Abil B8839 6,9 %Abil B8839 6.9%
Cyclopentasiloxan/CyclohexasiloxanCyclopentasiloxane / cyclohexasiloxane
Abil K4 6,9 %Abil K4 6.9%
Cyclotetrasiloxan/CyclopentasiloxanCyclotetrasiloxane / cyclopentasiloxane
Copolymer Nr. 28 1 ,5 %Copolymer No. 28 1.5%
B Aloxicoll L 40,0 %B Aloxicoll L 40.0%
Aluminium ChlorohydratAluminum chlorohydrate
Propylenglykol 25,0 %Propylene glycol 25.0%
Wasser dest. ad 100 %Distilled water ad 100%
Parfümöl q.s.Perfume oil q.s.
Herstellung: I Komponenten A und B separat mischenProduction: I Mix components A and B separately
II Phase B langsam unter Rühren bei Raumtemperatur zur Phase A geben.II Slowly add phase B to phase A while stirring at room temperature.
III HomogenisierenIII Homogenize
Beispiel 3: W/O-Antiperspirant CremeExample 3: W / O antiperspirant cream
A Abil EM90 2,0 %A Abil EM90 2.0%
Cetyldimethicon/CopolyolCetyl dimethicone / copolyol
Abil B 8839 20,0 %Abil B 8839 20.0%
Cyclopentasiloxan/CyclohexasiloxanCyclopentasiloxane / cyclohexasiloxane
Copolymer Nr. 65 2,0 %Copolymer No. 65 2.0%
B Aloxicoll L 17,0B Aloxicoll L 17.0
Aluminium ChlorohydratAluminum chlorohydrate
Wasser dest. ad 100 % Parfümöl q.s. Konservierungsmittel q.s.Distilled water ad 100% Perfume oil qs preservative qs
Herstellung:production:
I Phase B langsam unter Rühren bei Raumtemperatur zur Phase A geben.I Slowly add phase B to phase A while stirring at room temperature.
II HomogenisierenII homogenize
Beispiel 4: O/W-Deodorant Lotion A Teginacid H 3,0 % Glycerylstearat/Ceteth-20Example 4: O / W Deodorant Lotion A Teginacid H 3.0% Glyceryl Stearate / Ceteth-20
Tegosoft, fl. 3,0 % Cetearyl Octanoat Tegosoft CT 3,0 %Tegosoft, fl. 3.0% cetearyl octanoate Tegosoft CT 3.0%
Caprylic-/Caprictriglycerid Copolymer Nr. 30 0,75 %Caprylic / Caprictriglyceride Copolymer No. 30 0.75%
B Glycerin 3,0 % Wasser ad 100 C Zitronensäure 0,15 %B glycerin 3.0% water ad 100 C citric acid 0.15%
Konservierungsmittel q.s. Parfümöl q.s.Preservatives q.s. Perfume oil q.s.
Herstellung:production:
I Phase A und B separat auf ca. 80°C erhitzenI Heat phases A and B separately to approx. 80 ° C
II Phase A und Phase B zusammenführen III HomogenisierenII merge phase A and phase B III homogenize
IV Unter leichtem Rühren auf 30°C abkühlenIV Cool to 30 ° C with gentle stirring
V Phase C unterhalb von 40°C dazugebenV Add phase C below 40 ° C
Beispiel 5: Alkoholfreier Deodorant-Roll-on (opak)Example 5: Non-alcoholic deodorant roll-on (opaque)
A Tegodeo CW 90 2,0 %A Tegodeo CW 90 2.0%
Zinkricinoleat/Tetrahydroxypropyl- Ethylendiamin/Laureth-3/Propylenglykol Polyethylenglykol(3)laurylether 1 ,0 %Zinc ricinoleate / tetrahydroxypropyl-ethylenediamine / Laureth-3 / propylene glycol Polyethylene glycol (3) lauryl ether 1, 0%
Triethanolamin 1 ,0 % B Copolymer Nr. 18 1 ,2 %Triethanolamine 1.0% B Copolymer No. 18 1.2%
Wasser dest. ad 100 C Tagat R 40 3,0 %Distilled water ad 100 C Tagat R 40 3.0%
PEG-40 hydrogeniert.es Castor oilPEG-40 hydrogenated. Castor oil
Parfümöl q.s.Perfume oil q.s.
Konservierungsmittel q.s. D Zitronensäure (50%ig in Wasser) 0,2 %Preservatives q.s. D citric acid (50% in water) 0.2%
Herstellungmanufacturing
I Phasen A und B separat auf 80°C erwärmenI Heat phases A and B separately to 80 ° C
II Phase B in Phase A einrühren und homogenisierenII Stir phase B into phase A and homogenize
III Unter langsamem Rühren abkühlen IV Bei 30°C Phase C hinzufügenIII Cool with slow stirring IV Add phase C at 30 ° C
V Den pH-Wert mit Hilfe von Phase D einstellenV Adjust the pH using phase D.
Beispiel 6: Deo-Roll-onExample 6: Deodorant roll-on
A Copolymer Nr. 27 1 ,0 %A copolymer No. 27 1.0%
Wasser dest. ad 100 B Hydagen DCMF 0,1Distilled water ad 100 B Hydagen DCMF 0.1
Chitosanchitosan
Glykolsäure 1 ,5 % Glycerin (86%) 2,0 % Glycolic acid 1.5% glycerin (86%) 2.0%
Herstellung:production:
I Copolymer Nr. 27 unter starkem Rühren langsam in das Wasser geben, bis eine klare viskose Quellung entstanden ist.I Slowly add copolymer No. 27 into the water with vigorous stirring until a clear, viscous swelling has occurred.
II Komponenten der Phase B unter langsamem Rühren lösen pH 4 bis 5.II components of phase B dissolve pH 4 to 5 with slow stirring.
III Phase B in Phase A geben und homogen rührenIII Add phase B to phase A and stir until homogeneous
Beispiel 7: Deo-EmulsionExample 7: Deodorant emulsion
A Eumulgin B2 Flakes 1 ,0 %A Eumulgin B2 flakes 1, 0%
Ceteareth-20Ceteareth-20
Copolymer Nr. 35 1 ,0 %Copolymer No. 35 1.0%
Cetiol 5 5,0 %Cetiol 5 5.0%
Dioctylcyclohexane Cetiol OE 5,0 %Dioctylcyclohexane Cetiol OE 5.0%
DicaprylicetherDicaprylicether
Hydagen C.A.T. 2,0 %Hydagen C.A.T. 2.0%
Triethylcitrat B Hydagen DCMF 0,1 % ChitosanTriethyl citrate B Hydagen DCMF 0.1% chitosan
Glykolsäure 0,04 %Glycolic acid 0.04%
Wasser dest. Ad 100Distilled water Ad 100
Konservierungsmittel 2,0 %Preservative 2.0%
Herstellung:production:
I Die Komponenten der Phase A bei 80°C aufschmelze und homogenisierenI Melt the components of phase A at 80 ° C and homogenize
II Komponenten der Phase B unter Rühren lösen, und langsam unter Rühren zu A gebenII Dissolve phase B components with stirring, and slowly add to A while stirring
III Unter Rühren abkühlen IV Bei 30°C Konservierungsmittel zugeben Beispiel 8: Kristallklares alkoholfreies GelIII Cool with stirring IV Add preservative at 30 ° C Example 8: Crystal clear alcohol-free gel
A DC 3225 C 10,00 %A DC 3225 C 10.00%
Cyclomethicon/Dimethicon CopolyolCyclomethicone / Dimethicone Copolyol
DC 245 Fluid 3,40 %DC 245 fluid 3.40%
Cyclomethiconcyclomethicone
Polydimethylsiloxan 3,9 %Polydimethylsiloxane 3.9%
Dimethicondimethicone
Copolymer Nr. 53 0,75 %Copolymer No. 53 0.75%
Parfüm 52847 q.sPerfume 52847 q.s
B Rezal 36 G 44,0 %B Rezal 36 G 44.0%
Aluminum Zirconium Tetrachlorohydrex GLYAluminum zirconium tetrachlorohydrex GLY
Dipropylenglykol 20 %Dipropylene glycol 20%
Wasser dest. ad 100Distilled water ad 100
Herstellung:production:
I Komponenten A und B separat gut mischenI Mix components A and B separately well
II B zu A hinzufügenAdd II B to A.
III homogenisierenIII homogenize
Beispiel 9: O/W-Antiperspirant-CremeExample 9: O / W antiperspirant cream
A Copolymer Nr. 63 2,0 %A Copolymer No. 63 2.0%
Arlamol ISML 2,0 %Arlamol ISML 2.0%
Isosorbidlauratisosorbide
Dow Corning 245 Fluid 2,0 %Dow Corning 245 Fluid 2.0%
Cyclomethiconcyclomethicone
B Wasser dest. ad 100 %B distilled water ad 100%
Locron P (50 %ig) 40,0 %Locron P (50%) 40.0%
Aluminium ChlorohydratAluminum chlorohydrate
Konservierungsmittel q.sPreservative q.s
Parfüm q.s. HerstellungPerfume qs manufacturing
I Die Komponenten von A mischenI Mix the components of A.
II Unter Rühren B zu A geben II Add B to A while stirring

Claims

Patentansprüche claims
1. Deodorantien und Antiperspirantien, dadurch gekennzeichnet, dass sie mindestens ein Copolymer, erhältlich durch radikalische Copolymerisation von A) Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten,1. Deodorants and antiperspirants, characterized in that they contain at least one copolymer, obtainable by radical copolymerization of A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates,
B) gegebenenfalls einem oder mehreren weiteren olefinisch ungesättigten, nicht kationischen; gegebenenfalls vernetzenden, Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen, C) gegebenenfalls einem oder mehreren olefinisch ungesättigten, kationischen Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen,B) optionally one or more further olefinically unsaturated, non-cationic; optionally crosslinking comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol, C) optionally one or more olefinically unsaturated, cationic comonomers which have at least one oxygen, nitrogen, Have a sulfur or phosphorus atom and a molecular weight of less than 500 g / mol,
D) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, siliziumhaltigen Komponente(n),D) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization,
E) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, fluorhaltigen Komponente(n),E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization,
F) gegebenenfalls einem oder mehreren einfach oder mehrfach olefinisch ungesättigten, gegebenenfalls vernetzenden, Makromonomeren, die jeweils mindestens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom besitzen und ein zahlenmittleres Molekulargewicht größer oder gleich 200 g/mol aufweisen, wobei es sich bei den Makromonomeren nicht um eine siliziumhaltige Komponente D) oder fluorhaltige Komponente E) handelt,F) optionally one or more mono- or poly-olefinically unsaturated, optionally crosslinking, macromonomers, each having at least one oxygen, nitrogen, sulfur or phosphorus atom and having a number-average molecular weight greater than or equal to 200 g / mol, where it is in the Macromonomers are not silicon-containing component D) or fluorine-containing component E),
G) wobei die Copolymerisation gegebenenfalls in Gegenwart mindestens eines polymeren Additivs mit zahlenmittleren Molekulargewichten von 200 g/mol bis 109 g/mol erfolgt, H) mit der Maßgabe, dass die Komponente A) mit mindestens einerG) the copolymerization taking place if / is carried out in the presence of at least one polymeric additive having number average molecular weights of from 200 g / mol to 10 9 g mol, H) with the proviso that component A) with at least one
Komponente ausgewählt aus einer der Gruppen D) bis G) copolymerisiert wird, enthalten.Component selected from one of groups D) to G) is copolymerized.
2. Deodorantien und Antiperspirantien nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den Comonomeren B) um ungesättigte Carbonsäuren, Salze ungesättigter Carbonsäuren, Anhydride ungesättigter Carbonsäuren, Ester ungesättigter Carbonsäuren mit aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen Alkoholen mit 1 bis 22 C-Atomen, offenkettige N-Vinylamide, cyclische N-Vinylamide mit einer Ringgröße von 3 bis 9, Amide der Acrylsäure, Amide der Methacrylsäure, Amide substituierter Acrylsäuren, Amide substituierter Methacrylsäuren, 2-Vinylpyridin, 4-Vinylpyridin, Vinylacetat, Styrol, Acrylnitril, Vinylchlorid, Vinylidenchlorid, Tetrafluorethylen, Vinylphosphonsäure oder deren Ester oder Salze, Vinylsulfonsäure oder deren Ester oder Salze, Allylphosphonsäure oder deren Ester oder Salze und/oder Methallylsulfonsäure oder deren Ester oder Salze handelt.2. Deodorants and antiperspirants according to claim 1, characterized in that the comonomers B) are unsaturated Carboxylic acids, salts of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, esters of unsaturated carboxylic acids with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with 1 to 22 carbon atoms, open-chain N-vinylamides, cyclic N-vinylamides with a ring size of 3 to 9, amides acrylic acid, amides of methacrylic acid, amides of substituted acrylic acids, amides of substituted methacrylic acids, 2-vinylpyridine, 4-vinylpyridine, vinyl acetate, styrene, acrylonitrile, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or its esters or salts, vinylsulfonic acid or its esters or salts, allylphosphonic acid or their esters or salts and / or methallylsulfonic acid or their esters or salts.
3. Deodorantien und Antiperspirantien nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, dass es sich beiden Comonomeren C) um Diallyldimethylammoniumchlorid (DADMAC),3. Deodorants and antiperspirants according to claim 1 and / or 2, characterized in that the two comonomers C) are diallyldimethylammonium chloride (DADMAC),
[2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC),[2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),
[2-(Acryloyloxy)ethyl]trimethylammoniumchlorid,[2- (acryloyloxy) ethyl] trimethylammonium chloride,
[2-Methacrylamidoethyl]trimethylammoniumchlorid,[2-methacrylamidoethyl] trimethyl ammonium chloride,
[2-(Acrylamido)ethyI]trimethylammoniumchlorid, N-Methyl-2-vinylpyridiniumchlorid[2- (acrylamido) ethyl] trimethylammonium chloride, N-methyl-2-vinylpyridinium chloride
N-Methyl-4-vinylpyridiniumchloridN-methyl-4-vinyl pyridinium chloride
Dimethylaminoethylmethacrylat,dimethylaminoethyl
Dimethylaminopropylmethacrylamid,dimethylaminopropylmethacrylamide,
Methacryloylethyl-N-oxid und/oder Methacryloylethyl-betain handelt.Methacryloylethyl-N-oxide and / or methacryloylethyl-betaine.
4. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei den siliziumhaltigen Komponenten D) um Verbindungen der Formel (I)4. Deodorants and antiperspirants according to at least one of claims 1 to 3, characterized in that the silicon-containing components D) are compounds of the formula (I)
R1 - Z- [(Si(R3R4)-O-)w-(Si(R5R6)-O)x-]- R2 (I)R 1 - Z- [(Si (R 3 R 4 ) -O-) w - (Si (R 5 R 6 ) -O) x -] - R 2 (I)
handelt, wobei R1 einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl-, Methacryl-, Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder ein Styrylrest darstellt;acts where R 1 represents a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or a styryl radical;
Z eine chemische Brücke, bevorzugt ausgewählt aus -O-,Z is a chemical bridge, preferably selected from -O-,
-((Ci - C50) Alkylen)-, -((C6 - C30) Arylen)-, -((C5 - C8) Cycloalkylen)-, -((C1-C50) Alkenylen)-, -(Polypropylenoxid)n-, -(Polyethylenoxid).-,- ((Ci - C 50) alkylene) -, - ((C 6 - C 30) arylene) -, - ((C 5 - C 8) cycloalkylene) -, - ((C1-C50) alkenylene) -, - (Polypropylene oxide) n -, - (polyethylene oxide) .-,
-(Polypropylenoxid)n(Polyethylenoxid)o-, wobei n und o unabhängig voneinander Zahlen von 0 bis 200 bedeuten und die Verteilung der EO/PO- Einheiten statistisch oder blockförmig sein kann, -((C1 - C10) Alkyl)-(Si(OCH3)2)- und -(Si(OCH3)2)-, darstellt; R3, R4, R5 und R6 unabhängig voneinander -CH3, -O-CH3, -C6H5 oder -O-C6H5 bedeuten; w, x Zahlen von 0 bis 500 bedeuten, wobei entweder w oder x größer Null sein muss, und- (polypropylene oxide) n (polyethylene oxide) o-, where n and o independently of one another represent numbers from 0 to 200 and the distribution of the EO / PO units can be random or block-shaped, - ((C1 - C 10 ) alkyl) - ( Si (OCH 3 ) 2 ) - and - (Si (OCH 3 ) 2 ) -,; R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -O-CH 3 , -C 6 H 5 or -OC 6 H 5 ; w, x mean numbers from 0 to 500, where either w or x must be greater than zero, and
R2 einen gesättigten oder ungesättigten, aliphatischen, cycloaliphatischen, arylaliphatischen oder aromatischen Rest mit jeweils 1 bis 50 C-Atomen oder eine Gruppe der Formeln -OH, -NH2, -N(CH3)2 , -R7 oder eine Gruppe - Z-R1 bedeutet, wobei Z und R1 die obengenannten Bedeutungen haben und R7 eine Gruppe der Formel -O-Si(CH3)3, -O-Si(Phenyl)3, -O-Si(O-Si(CH3)3)2CH3) und -O-Si(O-Si(Ph)3)2Ph) bedeutet.R 2 is a saturated or unsaturated, aliphatic, cycloaliphatic, arylaliphatic or aromatic radical each having 1 to 50 C atoms or a group of the formulas -OH, -NH 2 , -N (CH 3 ) 2, -R 7 or a group - ZR 1 means, where Z and R 1 have the meanings given above and R 7 is a group of the formula -O-Si (CH 3 ) 3 , -O-Si (phenyl) 3 , -O-Si (O-Si (CH 3 ) 3 ) 2CH 3 ) and -O-Si (O-Si (Ph) 3 ) 2 Ph) means.
5. Mittel nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich bei den fluorhaltigen Komponenten E) um5. Composition according to at least one of claims 1 to 4, characterized in that it is the fluorine-containing components E)
Verbindungen der Formel (II)Compounds of formula (II)
R1-Y-CrH2rCsF2sCF3 (II) handelt, wobei R1 eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen, bevorzugt einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl-, Methacryl-, Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest, darstellt;R 1 -YC r H 2r C s F 2s CF 3 (II), where R 1 is a polymerizable function from the group of vinylically unsaturated compounds, preferably a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic -, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or styryl radical;
Y eine chemische Brücke, bevorzugt -O-, -C(O)-, -C(O)-O-, -S-, -O-CH2-CH(O-)-CH2OH, -O-CH2-CH(OH)-CH2-O-, -O-SO2-O-, -O-S(O)-O-, -PH-, -P(CH3)-, -PO3-, -NH-, -N(CH3)-, -O-(C1-C60)Alkyl-O-, -O-Phenyl-O-, -O-Benzyl-O-, -O-(C5-C8)Cycloalkyl-O-, -O-Cd-CsoJAlkenyl-O-, -O-(CH(CH3)-CH2-O)n-, -O-(CH2-CH2-O)π- und -O-([CH-CH2-O]π-[CH2-CH2-O]m)0-, wobei n, m und o unabhängig voneinander Zahlen von 0 bis 200 bedeuten, darstellt und r, s stöchiometrische Koeffizienten darstellen, die unabhängig voneinander Zahlen zwischen 0 und 200 sind.Y is a chemical bridge, preferably -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 -CH (OH) -CH 2 -O-, -O-SO 2 -O-, -OS (O) -O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH -, -N (CH 3 ) -, -O- (C 1 -C 60 ) alkyl-O-, -O-phenyl-O-, -O-benzyl-O-, -O- (C 5 -C 8 ) cycloalkyl-O-, -O-Cd-CsoJAlkenyl-O-, -O- (CH (CH 3 ) -CH 2 -O) n -, -O- (CH 2 -CH 2 -O) π - and -O - ([CH-CH2-O] π - [CH 2 -CH 2 -O] m ) 0 - , where n, m and o independently represent numbers from 0 to 200, and r, s represent stoichiometric coefficients which are independently numbers between 0 and 200.
6. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es sich bei den Makromonomeren F) um Verbindungen der Formel (III) handelt,6. Deodorants and antiperspirants according to at least one of claims 1 to 5, characterized in that the macromonomers F) are compounds of the formula (III),
R1 - Y - [(A)v - (B)w - (C)χ - (D)z] - R2 (III)R 1 - Y - [(A) v - (B) w - (C) χ - (D) z ] - R 2 (III)
wobei R1 eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen, bevorzugt einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl-, Methacryl-, Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest, darstellt;where R 1 is a polymerizable function from the group of vinylically unsaturated compounds, preferably a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or styryl radical , represents;
Y eine verbrückende Gruppe, bevorzugt -O-, -S-, -C(O)-, -C(O)-O-, -O-CH2-CH(O-)-CH2OH, -O-CH2-CH(OH)-CH2O-, -O-SO2-O-, -O-SO2-O-, -O-SO- O-, -PH-, -P(CH3)-, -PO3-, -NH- und -N(CH3)- darstellt;Y is a bridging group, preferably -O-, -S-, -C (O) -, -C (O) -O-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 -CH (OH) -CH 2 O-, -O-SO 2 -O-, -O-SO 2 -O-, -O-SO- O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH- and -N (CH 3 ) -;
A, B, C und D unabhängig voneinander diskrete chemische Wiederholungseinheiten, bevorzugt hervorgegangen aus Acrylamid, Methacrylamid, Ethylenoxid, Propylenoxid, AMPS, Acrylsäure, Methacrylsäure, Methylmethacrylat, Acrylnitril, Maleinsäure, Vinylacetat, Styrol, 1 ,3-Butadien, Isopren, Isobuten, Diethylacrylamid und Diisopropylacrylamid, insbesondere bevorzugt Ethylenoxid, Propylenoxid darstellen; v, w, x und z unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, betragen, wobei die Summe aus v, w, x und z im Mittel > 1 ist; und R2 einen linearen oder verzweigten aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (Cι-C5o)-Kohlenwasserstoffrest, OH, -NH2 oder -N(CH3)2 darstellt oder gleich [-Y-R1] ist. A, B, C and D independently of one another discrete chemical repeat units, preferably originating from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1, 3-butadiene, isoprene, isobutene, Diethylacrylamide and diisopropylacrylamide, particularly preferably ethylene oxide, propylene oxide; v, w, x and z independently of one another are 0 to 500, preferably 1 to 30, the sum of v, w, x and z being> 1 on average; and R 2 represents a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 5 o) hydrocarbon radical, OH, -NH 2 or -N (CH 3 ) 2 or is equal to [-YR 1 ].
7. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es sich bei den polymeren Additiven G) um Homo- oder Copolymere aus N-Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon, Ethylenoxid, Propylenoxid, Acryloyldimethyltaurinsäure, N-Vinylcaprolactam, N-Vinylmethylacetamid, Acrylamid, Acrylsäure, Methacrylsäure, N-Vinylmorpholid, Hydroxymethylmethacrylat, Diallyldimethylammoniumchlorid (DADMAC) und/oder [2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC); Polyalkylenglykole und/oder Alkylpolyglykole handelt.7. Deodorants and antiperspirants according to at least one of claims 1 to 6, characterized in that the polymeric additives G) are homo- or copolymers of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N-vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxymethyl methacrylate, diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.
8. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Copolymerisation in Gegenwart mindestens eines polymeren Additivs G) erfolgt.8. Deodorants and antiperspirants according to at least one of claims 1 to 7, characterized in that the copolymerization takes place in the presence of at least one polymeric additive G).
9. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Copolymere vernetzt sind.9. Deodorants and antiperspirants according to at least one of claims 1 to 8, characterized in that the copolymers are crosslinked.
10. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Copolymere durch Fällungspolymerisation in tert.-Butanol hergestellt werden.10. Deodorants and antiperspirants according to at least one of claims 1 to 9, characterized in that the copolymers are prepared by precipitation polymerization in tert-butanol.
11. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Copolymere wasserlöslich oder wasserquellbar sind.11. Deodorants and antiperspirants according to at least one of claims 1 to 10, characterized in that the copolymers are water-soluble or water-swellable.
12. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass sie, bezogen auf die fertigen Mittel, 0,01 bis 10 Gew.-% der Copolymere enthalten.12. Deodorants and antiperspirants according to at least one of claims 1 to 11, characterized in that they contain, based on the finished agent, 0.01 to 10 wt .-% of the copolymers.
13. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass sie 0,01 bis 89 Gew.-% Wasser enthalten.13. Deodorants and antiperspirants according to at least one of claims 1 to 12, characterized in that they contain 0.01 to 89 wt .-% water.
14. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass sie bis 10 Gew.-% Glycerin enthalten. 14. Deodorants and antiperspirants according to at least one of claims 1 to 13, characterized in that they contain up to 10 wt .-% glycerol.
15. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass sie antimikrobielle Wirkstoffe enthalten.15. Deodorants and antiperspirants according to at least one of claims 1 to 14, characterized in that they contain antimicrobial agents.
16. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass sie Adstringenzien enthalten.16. Deodorants and antiperspirants according to at least one of claims 1 to 15, characterized in that they contain astringents.
17. Deodorantien und Antiperspirantien nach mindestens einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass es sich dabei um Lotionen, Cremes, Stifte, Mehrphasenstifte, Sprays, Roll-On-Präparate oder Puder handelt. 17. Deodorants and antiperspirants according to at least one of claims 1 to 16, characterized in that these are lotions, creams, sticks, multi-phase sticks, sprays, roll-on preparations or powder.
EP01989525A 2000-12-01 2001-11-28 Deodorants and anti-perspirants Expired - Lifetime EP1432746B1 (en)

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